Oral Care Compositions

ABSTRACT

Provided are aqueous soluble tin phosphate complexes formed from a mixture comprising tin (II) fluoride or tin (II) chloride and a tripolyphosphate salt, e.g., sodium tripolyphosphate (Na 5 P 3 O 10 ), and oral care compositions comprising the complex and uses thereof.

This application claims priority to U.S. Provisional Application No. 62/273,304 filed Dec. 30, 2015, which is hereby incorporated by reference in its entirety.

BACKGROUND

Dentinal hypersensitivity is acute, localized tooth pain in response to physical stimulation of the dentine surface by thermal (hot or cold), osmotic, tactile, and/or a combination of thermal, osmotic, and tactile stimulation of the exposed dentin. Exposure of the dentine, which is generally due to recession of the gums, or loss of enamel, frequently leads to hypersensitivity. Dentinal tubules open to the surface have a high correlation with dentinal hypersensitivity. Dentinal tubules lead from the pulp to the cementum. When the surface cementum of the tooth root is eroded, the dentinal tubules become exposed to the external environment. The exposed dentinal tubules provide a pathway for transmission of fluid flow to the pulpal nerves, the transmission induced by changes in temperature, pressure, and ionic gradients.

To relieve dentinal hypersensitivity, dentinal tubules may be plugged. Such occlusion may be carried out either by blocking the tubule with a particle of smaller size than the tubule or by inducing precipitation within the dentin tubule itself.

Tin (II) fluoride (also known as stannous fluoride, SnF₂) has been used in oral care compositions, but has disadvantages. Tin (II) may react with other ingredients of the oral care composition to form insoluble inactive tin compounds, thereby reducing the effective amount of available tin (II) in the composition. In addition, tin (II) fluoride may cause yellow-brown tooth staining and may impart unacceptable astringency to the composition.

While the prior art discloses the use of various oral compositions for the treatment of dentinal hypersensitivity, there is still a need for additional compositions and methods that provide improved performance in such treatments.

BRIEF SUMMARY

Tin (II) fluoride is soluble in water, however, it oxidizes to form insoluble precipitates of tin. In addition, tin can form water insoluble compounds with phosphates.

It has now been discovered that tin (II) fluoride and tin (II) chloride form aqueous soluble tin phosphate complexes upon mixture with a tripolyphosphate salt, e.g., an alkali tripolyphosphate salt, e.g., potassium tripolyphosphate (K₅P₃O₁₀) or sodium tripolyphosphate (Na₅P₃O₁₀) (STPP).

When the complexes are placed in an oral care composition, the oral care composition, upon use, may provide a precipitate that can plug dentinal tubules, thereby reducing the sensitivity of the teeth. While providing efficient delivery of tin in comparison to compositions with insoluble tin salts, the compositions comprising the tin phosphate complexes may not exhibit the instability, tooth staining, and poor taste associated with conventional tin-based oral care products using soluble tin salts.

Provided are aqueous soluble tin phosphate complexes, e.g., formed from a mixture comprising tin (II) fluoride or tin (II) chloride and a tripolyphosphate salt, e.g., an alkali tripolyphosphate salt, e.g., potassium tripolyphosphate (K₅P₃O₁₀) or sodium tripolyphosphate (Na₅P₃O₁₀), e.g., sodium tripolyphosphate (Na₅P₃O₁₀).

Also provided are oral care compositions, e.g., mouthwashes, oral gels, or dentifrices, comprising the aqueous soluble tin phosphate complexes. The compositions may be formulated in a suitable oral care composition, e.g., a mouthwash, oral gel, or dentifrice, for example comprising one or more abrasives, surfactants, foaming agents, vitamins, enzymes, humectants, thickeners, antimicrobial agents, whitening agents, pH agents, preservatives, flavorings, and/or colorants.

Further provided are mouthwashes comprising the aqueous soluble tin phosphate complexes, which are clear when formulated, but which provide a precipitate when contacted with saliva.

Further provided are methods of using the oral care compositions to reduce or inhibit dentinal hypersensitivity comprising applying the composition to teeth.

Further provided is a method of occluding dentin tubules comprising applying the oral care compositions to teeth.

Further provided are methods of using the oral care compositions to reduce or inhibit one or more of dental caries (i.e., cavities), gingivitis, and plaque comprising applying the composition to teeth.

Further provided are methods of making the aqueous soluble tin phosphate complexes comprising combining tin (II) fluoride or tin (II) chloride and a tripolyphosphate salt, e.g., an alkali tripolyphosphate salt, e.g., sodium tripolyphosphate, in aqueous solution, e.g., at a molar ratio of 1P:1Sn to less than 15P:1Sn, e.g., greater than 1P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to 10P:1Sn, e.g., 2P:1Sn to 5P:1Sn; optionally isolating the complexes thus formed as a solid.

Further provided are methods of making the oral care compositions comprising admixing the aqueous soluble tin phosphate complexes with an oral care base, e.g., a mouthwash, oral gel, or dentifrice base.

Further areas of applicability of the present invention will become apparent from the detailed description provided hereinafter. It should be understood that the detailed description and specific examples, while indicating preferred embodiments of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

The present invention will become more fully understood from the detailed description and the accompanying drawings, wherein:

FIG. 1 depicts Fourier transform infrared spectra.

FIG. 2 depicts Fourier transform infrared spectra.

FIG. 3 depicts Raman spectra of water, STPP, and solutions with P:Sn molar ratios of 2, 5, and 10 (from top to bottom: STPP, P:Sn molar ratio 10, P:Sn molar ratio 5, P:Sn molar ratio 2, and water).

FIG. 4 depicts ³¹P NMR spectra of solutions with P:Sn molar ratios of 10 (A), 5 (B), and 2 (C).

FIG. 5 depicts ¹¹⁹Sn NMR spectra of solutions with P:Sn molar ratios of 10 (A), 5 (B), and 2 (C).

FIG. 6 is a Fourier transform infrared spectrum of SnF₂.

FIG. 7 depicts a ³¹P NMR spectrum of a solution of STPP.

DETAILED DESCRIPTION

The following description of the preferred embodiment(s) is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses.

As used throughout, ranges are used as shorthand for describing each and every value that is within the range. Any value within the range can be selected as the terminus of the range. In addition, all references cited herein are hereby incorporated by reference in their entireties. In the event of a conflict in a definition in the present disclosure and that of a cited reference, the present disclosure controls.

Unless otherwise specified, all percentages and amounts expressed herein and elsewhere in the specification should be understood to refer to percentages by weight. The amounts given are based on the active weight of the material.

Provided is an aqueous soluble tin phosphate complex (Complex 1), e.g.,

-   -   1.1 Complex 1, wherein the complex is formed from a mixture         comprising tin (II) fluoride and a tripolyphosphate salt, e.g.,         an alkali tripolyphosphate salt, e.g., potassium         tripolyphosphate (K₅P₃O₁₀) or sodium tripolyphosphate         (Na₅P₃O₁₀).     -   1.2 Complex 1, wherein the complex is formed from a mixture         comprising tin (II) chloride and a tripolyphosphate salt, e.g.,         an alkali tripolyphosphate salt, e.g., potassium         tripolyphosphate (K₅P₃O₁₀) or sodium tripolyphosphate         (Na₅P₃O₁₀).     -   1.3 Complex 1 or 1.1, wherein the complex is formed from a         mixture comprising tin (II) fluoride and a tripolyphosphate         salt, e.g., an alkali tripolyphosphate salt, e.g., potassium         tripolyphosphate (K₅P₃O₁₀) or sodium tripolyphosphate         (Na₅P₃O₁₀), in an aqueous solution.     -   1.4 Complex 1 or 1.2 wherein the complex is formed from a         mixture comprising tin (II) chloride and a tripolyphosphate         salt, e.g., an alkali tripolyphosphate salt, e.g., potassium         tripolyphosphate (K₅P₃O₁₀) or sodium tripolyphosphate         (Na₅P₃O₁₀), in an aqueous solution.     -   1.5 Complex 1.3, wherein the aqueous solution has a pH from 4-9,         e.g., from 5-8, e.g., from 5-7, e.g., from 5-6, e.g., from 6-8,         e.g., from 6-7, e.g., from 7-8.     -   1.6 Complex 1.4, wherein the aqueous solution has a pH from 4-9,         e.g., from 4-8, e.g., from 4-7, e.g., from 5-8, e.g., from 6-8,         e.g., from 5-7, e.g., from 4-6, e.g., from 4-5, e.g., from 5-6,         e.g., from 6-7, e.g., from 7-8.     -   1.7 Any of Complexes 1, 1.1, 1.3, or 1.5, wherein the complex is         formed from a mixture comprising tin (II) fluoride and sodium         tripolyphosphate (Na₅P₃O₁₀).     -   1.8 Any of Complexes 1, 1.2, 1.4, or 1.6, wherein the complex is         formed from a mixture comprising tin (II) chloride and sodium         tripolyphosphate (Na₅P₃O₁₀).     -   1.9 Any of the foregoing complexes, wherein the complex exhibits         a Fourier transform infrared spectrum substantially as shown in         the Sn-STPP spectrum in FIG. 1.     -   1.10 Any of the foregoing complexes, wherein the complex         exhibits a Fourier transform infrared spectrum substantially as         shown in the Sn-STPP spectrum in FIG. 2.     -   1.11 Any of the foregoing complexes, wherein the complex         exhibits a Fourier transform infrared spectrum comprising one or         more peaks selected from the group consisting of: 1077 cm⁻¹, 963         cm⁻¹, 881 cm⁻¹, and 704 cm⁻¹.     -   1.12 Any of the foregoing complexes, wherein the complex         exhibits a Fourier transform infrared spectrum comprising one or         more peaks selected from the group consisting of: 2233 cm⁻¹,         1077 cm⁻¹, 963 cm⁻¹, 881 cm⁻¹, and 704 cm⁻¹.     -   1.13 Any of the foregoing complexes, wherein the complex         exhibits a Fourier transform infrared spectrum comprising one or         more peaks selected from the group consisting of: 3257 cm⁻¹,         2233 cm⁻¹, 1648 cm⁻¹, 1077 cm⁻¹, 963 cm⁻¹, 881 cm⁻¹, and 704         cm⁻¹.     -   1.14 Any of the foregoing complexes, wherein the complex         exhibits a Fourier transform infrared spectrum comprising the         following peaks: 1077 cm⁻¹, 963 cm⁻¹, 881 cm⁻¹, and 704 cm⁻¹.     -   1.15 Any of the foregoing complexes, wherein the complex         exhibits a Fourier transform infrared spectrum comprising the         following peaks: 3257 cm⁻¹, 1648 cm⁻¹, 1077 cm⁻¹, 963 cm⁻¹, 881         cm⁻¹, and 704 cm⁻¹.     -   1.16 Any of the foregoing complexes, wherein the complex         exhibits a Fourier transform infrared spectrum comprising the         following peaks: 2233 cm⁻¹, 1077 cm⁻¹, 963 cm⁻¹, 881 cm⁻¹, and         704 cm⁻¹.     -   1.17 Any of the foregoing complexes, wherein the complex         exhibits a Fourier transform infrared spectrum comprising the         following peaks: 3257 cm⁻¹, 2233 cm⁻¹, 1648 cm⁻¹, 1077 cm⁻¹, 963         cm⁻¹, 881 cm⁻¹, and 704 cm⁻¹.     -   1.18 Any of the foregoing complexes, wherein the complex         exhibits a Fourier transform infrared spectrum comprising one or         more peaks selected from the group consisting of: 1081 cm⁻¹, 969         cm⁻¹, 883 cm⁻¹, 733 cm⁻¹, and 512 cm⁻¹.     -   1.19 Any of the foregoing complexes, wherein the complex         exhibits a Fourier transform infrared spectrum comprising the         following peaks: 1081 cm⁻¹, 969 cm⁻¹, 883 cm⁻¹, 733 cm⁻¹, and         512 cm⁻¹.     -   1.20 Any of the foregoing complexes, wherein the complex         exhibits a Raman spectrum substantially as shown in any of the         P/Sn Raman spectra of FIG. 3.     -   1.21 Any of the foregoing complexes, wherein the complex         exhibits a Raman spectrum comprising one or more peaks selected         from the group consisting of: 719 cm⁻¹ and 1084 cm⁻¹.     -   1.22 Any of the foregoing complexes, wherein the complex         exhibits a Raman spectrum comprising the following peaks: 719         cm⁻¹ and 1084 cm⁻¹.     -   1.23 Any of the foregoing complexes, wherein the complex         exhibits a Raman spectrum comprising one or more peaks selected         from the group consisting of: 719 cm⁻¹, 978 cm⁻¹, and 1084 cm⁻¹.     -   1.24 Any of the foregoing complexes, wherein the complex         exhibits a Raman spectrum comprising the following peaks: 719         cm⁻¹, 978 cm⁻¹, and 1084 cm⁻¹.     -   1.25 Any of the foregoing complexes, wherein the complex         exhibits a Raman spectrum comprising one or more peaks selected         from the group consisting of: 712 cm⁻¹, 978 cm⁻¹, and 1094 cm⁻¹.     -   1.26 Any of the foregoing complexes, wherein the complex         exhibits a Raman spectrum comprising the following peaks: 712         cm⁻¹, 978 cm⁻¹, and 1094 cm⁻¹.     -   1.27 Any of the foregoing complexes, wherein the complex         exhibits a ³¹P NMR spectrum as shown in any of the NMR spectra         of FIG. 4, A, 4, B, or 4, C, wherein the NMR spectrum is         obtained on an aqueous solution with 5 weight % D₂O added and is         externally referenced to 85% H₃PO₄ set to 0 ppm.     -   1.28 Any of the foregoing complexes, wherein the complex         exhibits a ³¹P NMR spectrum comprising one or more peaks         selected from the group consisting of: −6 ppm (doublet) and −19         ppm (triplet), e.g., −6.2 ppm (doublet), −6.3 ppm (doublet),         −19.1 ppm (triplet), −19.2 ppm (triplet), and −19.3 ppm         (triplet), e.g., −6.24 ppm (doublet), −6.33 ppm (doublet),         −19.08 ppm (triplet), −19.17 ppm (triplet), and −19.27 ppm         (triplet), wherein the NMR spectrum is obtained on an aqueous         solution with 5 weight % D₂O added and is externally referenced         to 85% H₃PO₄ set to 0 ppm.     -   1.29 Any of the foregoing complexes, wherein the complex         exhibits a ³¹P NMR spectrum comprising the following peaks: −6         ppm (doublet) and −19 ppm (triplet), e.g., −6.2 ppm (doublet),         −6.3 ppm (doublet), −19.1 ppm (triplet), −19.2 ppm (triplet),         and −19.3 ppm (triplet), e.g., −6.24 ppm (doublet), −6.33 ppm         (doublet), −19.08 ppm (triplet), −19.17 ppm (triplet), and         −19.27 ppm (triplet), wherein the NMR spectrum is obtained on an         aqueous solution with 5 weight % D₂O added and is externally         referenced to 85% H₃PO₄ set to 0 ppm.     -   1.30 Any of the foregoing complexes, wherein the complex         exhibits a ³¹P NMR spectrum comprising one or more peaks         selected from the group consisting of: 2 ppm, −6 ppm (doublet),         −7 ppm, and −19 ppm (triplet), e.g., 2.2 ppm, −6.2 ppm         (doublet), −6.3 ppm (doublet), −6.7 ppm, −19.1 ppm (triplet),         −19.2 ppm (triplet), and −19.3 ppm (triplet), e.g., 2.21 ppm,         −6.24 ppm (doublet), −6.33 ppm (doublet), −6.68 ppm, −19.08 ppm         (triplet), −19.17 ppm (triplet), and −19.27 ppm (triplet),         wherein the NMR spectrum is obtained on an aqueous solution with         5 weight % D₂O added and is externally referenced to 85% H₃PO₄         set to 0 ppm.     -   1.31 Any of the foregoing complexes, wherein the complex         exhibits a ³¹P NMR spectrum comprising the following peaks: 2         ppm, −6 ppm (doublet), −7 ppm, and −19 ppm (triplet), e.g., 2.2         ppm, −6.2 ppm (doublet), −6.3 ppm (doublet), −6.7 ppm, −19.1 ppm         (triplet), −19.2 ppm (triplet), and −19.3 ppm (triplet), e.g.,         2.21 ppm, −6.24 ppm (doublet), −6.33 ppm (doublet), −6.68 ppm,         −19.08 ppm (triplet), −19.17 ppm (triplet), and −19.27 ppm         (triplet), wherein the NMR spectrum is obtained on an aqueous         solution with 5 weight % D₂O added and is externally referenced         to 85% H₃PO₄ set to 0 ppm.     -   1.32 Any of the foregoing complexes, wherein the complex         exhibits a ³¹P NMR spectrum comprising one or more peaks         selected from the group consisting of: −8 ppm (doublet) and −19         ppm (triplet), e.g., −7.5 ppm (doublet), −7.6 ppm (doublet),         −19.1 ppm (triplet), −19.2 ppm (triplet), and −19.3 ppm         (triplet), e.g., −7.52 ppm (doublet), −7.62 ppm (doublet),         −19.09 ppm (triplet), −19.19 ppm (triplet), and −19.29 ppm         (triplet), wherein the NMR spectrum is obtained on an aqueous         solution with 5 weight % D₂O added and is externally referenced         to 85% H₃PO₄ set to 0 ppm.     -   1.33 Any of the foregoing complexes, wherein the complex         exhibits a ³¹P NMR spectrum comprising the following peaks: −8         ppm (doublet) and −19 ppm (triplet), e.g., −7.5 ppm (doublet),         −7.6 ppm (doublet), −19.1 ppm (triplet), −19.2 ppm (triplet),         and −19.3 ppm (triplet), e.g., −7.52 ppm (doublet), −7.62 ppm         (doublet), −19.09 ppm (triplet), −19.19 ppm (triplet), and         −19.29 ppm (triplet), wherein the NMR spectrum is obtained on an         aqueous solution with 5 weight % D₂O added and is externally         referenced to 85% H₃PO₄ set to 0 ppm.     -   1.34 Any of the foregoing complexes, wherein the complex         exhibits a ³¹P NMR spectrum comprising one or more peaks         selected from the group consisting of: 2 ppm, −7 ppm, −8 ppm         (doublet), −10 ppm, −11 ppm, −12 ppm, and −19 ppm (triplet),         e.g., 1.7 ppm, −7.3 ppm, −7.5 ppm (doublet), −7.6 ppm (doublet),         −9.9 ppm, −10.4 ppm, −10.8 ppm, −11.6 ppm, −19.1 ppm (triplet),         −19.2 ppm (triplet), and −19.3 ppm (triplet), e.g., 1.73 ppm,         −7.27 ppm, −7.52 ppm (doublet), −7.62 ppm (doublet), −9.89 ppm,         −10.37 ppm, −10.83 ppm, −11.62 ppm, −19.09 ppm (triplet), −19.19         ppm (triplet), and −19.29 ppm (triplet), wherein the NMR         spectrum is obtained on an aqueous solution with 5 weight % D₂O         added and is externally referenced to 85% H₃PO₄ set to 0 ppm.     -   1.35 Any of the foregoing complexes, wherein the complex         exhibits a ³¹P NMR spectrum comprising the following peaks: 2         ppm, −7 ppm, −8 ppm (doublet), −10 ppm, −11 ppm, −12 ppm, and         −19 ppm (triplet), e.g., 1.7 ppm, −7.3 ppm, −7.5 ppm (doublet),         −7.6 ppm (doublet), −9.9 ppm, −10.4 ppm, −10.8 ppm, −11.6 ppm,         −19.1 ppm (triplet), −19.2 ppm (triplet), and −19.3 ppm         (triplet), e.g., 1.73 ppm, −7.27 ppm, −7.52 ppm (doublet), −7.62         ppm (doublet), −9.89 ppm, −10.37 ppm, −10.83 ppm, −11.62 ppm,         −19.09 ppm (triplet), −19.19 ppm (triplet), and −19.29 ppm         (triplet), wherein the NMR spectrum is obtained on an aqueous         solution with 5 weight % D₂O added and is externally referenced         to 85% H₃PO₄ set to 0 ppm.     -   1.36 Any of the foregoing complexes, wherein the complex         exhibits a ³¹P NMR spectrum comprising one or more peaks         selected from the group consisting of: −8 ppm (doublet) and −18         ppm (triplet), e.g., −8.3 ppm (doublet), −8.4 ppm (doublet),         −17.7 ppm (triplet), −17.8 ppm (triplet), and −17.9 ppm         (triplet), e.g., −8.27 ppm (doublet), −8.37 ppm (doublet),         −17.69 ppm (triplet), −17.79 ppm (triplet), and −17.89 ppm         (triplet), wherein the NMR spectrum is obtained on an aqueous         solution with 5 weight % D₂O added and is externally referenced         to 85% H₃PO₄ set to 0 ppm.     -   1.37 Any of the foregoing complexes, wherein the complex         exhibits a ³¹P NMR spectrum comprising the following peaks: −8         ppm (doublet) and −18 ppm (triplet), e.g., −8.3 ppm (doublet),         −8.4 ppm (doublet), −17.7 ppm (triplet), −17.8 ppm (triplet),         and −17.9 ppm (triplet), e.g., −8.27 ppm (doublet), −8.37 ppm         (doublet), −17.69 ppm (triplet), −17.79 ppm (triplet), and         −17.89 ppm (triplet), wherein the NMR spectrum is obtained on an         aqueous solution with 5 weight % D₂O added and is externally         referenced to 85% H₃PO₄ set to 0 ppm.     -   1.38 Any of the foregoing complexes, wherein the complex         exhibits a ³¹P NMR spectrum comprising one or more peaks         selected from the group consisting of: −8 ppm (doublet), −9 ppm,         and −18 ppm (triplet), e.g., −8.3 ppm (doublet), −8.4 ppm         (doublet), −9.1 ppm, −17.7 ppm (triplet), −17.8 ppm (triplet),         and −17.9 ppm (triplet), e.g., −8.27 ppm (doublet), −8.37 ppm         (doublet), −9.07 ppm, −17.69 ppm (triplet), −17.79 ppm         (triplet), and −17.89 ppm (triplet), wherein the NMR spectrum is         obtained on an aqueous solution with 5 weight % D₂O added and is         externally referenced to 85% H₃PO₄ set to 0 ppm.     -   1.39 Any of the foregoing complexes, wherein the complex         exhibits a ³¹P NMR spectrum comprising the following peaks: −8         ppm (doublet), −9 ppm, and −18 ppm (triplet), e.g., −8.3 ppm         (doublet), −8.4 ppm (doublet), −9.1 ppm, −17.7 ppm (triplet),         −17.8 ppm (triplet), and −17.9 ppm (triplet), e.g., −8.27 ppm         (doublet), −8.37 ppm (doublet), −9.07 ppm, −17.69 ppm (triplet),         −17.79 ppm (triplet), and −17.89 ppm (triplet), wherein the NMR         spectrum is obtained on an aqueous solution with 5 weight % D₂O         added and is externally referenced to 85% H₃PO₄ set to 0 ppm.     -   1.40 Any of the foregoing complexes, wherein the complex         exhibits a ¹¹⁹Sn NMR spectrum as shown in any of the NMR spectra         of FIG. 5, A, 5, B, or 5, C, wherein the NMR spectrum is         obtained on an aqueous solution with 5 weight % D₂O added and is         externally referenced to saturated SnF₂ in D₂O at −796 ppm.     -   1.41 Any of the foregoing complexes, wherein the complex         exhibits a ¹¹⁹Sn NMR spectrum comprising the following peak:         −688 ppm, e.g., −687.9 ppm, e.g., −687.87 ppm, wherein the NMR         spectrum is obtained on an aqueous solution with 5 weight % D₂O         added and is externally referenced to saturated SnF₂ in D₂O at         −796 ppm.     -   1.42 Any of the foregoing complexes, wherein the complex         exhibits a ¹¹⁹Sn NMR spectrum comprising the following peak:         −700 ppm, e.g., −699.5 ppm, e.g., −699.51 ppm, wherein the NMR         is obtained on an aqueous solution with 5 weight % D₂O added and         is externally referenced to saturated SnF₂ in D₂O at −796 ppm.     -   1.43 Any of the foregoing complexes, wherein the complex         exhibits a ¹¹⁹Sn NMR spectrum comprising one or more peaks         selected from the group consisting of: −685 ppm, −692 ppm, −700         ppm, −714 ppm, −717 ppm, −723 ppm, −725 ppm, and −733 ppm, e.g.,         −684.6 ppm, −691.7 ppm, −699.5 ppm, −714.3 ppm, −717.3 ppm,         −723.0 ppm, −725.3 ppm, and −732.6 ppm, e.g., −684.61 ppm,         −691.73 ppm, −699.51 ppm, −714.30 ppm, −717.32 ppm, −723.01 ppm,         −725.28 ppm, and −732.59 ppm, wherein the NMR spectrum is         obtained on an aqueous solution with 5 weight % D₂O added and is         externally referenced to saturated SnF₂ in D₂O at −796 ppm.     -   1.44 Any of the foregoing complexes, wherein the complex         exhibits a ¹¹⁹Sn NMR spectrum comprising the following peaks:         −685 ppm, −692 ppm, −700 ppm, −714 ppm, −717 ppm, −723 ppm, −725         ppm, and −733 ppm, e.g., −684.6 ppm, −691.7 ppm, −699.5 ppm,         −714.3 ppm, −717.3 ppm, −723.0 ppm, −725.3 ppm, and −732.6 ppm,         e.g., −684.61 ppm, −691.73 ppm, −699.51 ppm, −714.30 ppm,         −717.32 ppm, −723.01 ppm, −725.28 ppm, and −732.59 ppm, wherein         the NMR spectrum is obtained on an aqueous solution with 5         weight % D₂O added and is externally referenced to saturated         SnF₂ in D₂O at −796 ppm.     -   1.45 Any of the foregoing complexes, wherein the complex         exhibits a ¹¹⁹Sn NMR spectrum comprising the following peak:         −715 ppm, e.g., −715.0 ppm, e.g., −714.97 ppm, wherein the NMR         spectrum is obtained on an aqueous solution with 5 weight % D₂O         added and is externally referenced to saturated SnF₂ in D₂O at         −796 ppm.     -   1.46 Any of the foregoing complexes, wherein the complex is         formed from a mixture comprising tin (II) fluoride or tin (II)         chloride and the tripolyphosphate salt, e.g., alkali         tripolyphosphate salt, in a molar ratio of 1P:1Sn to less than         15P:1Sn, e.g., greater than 1P:1Sn to less than 15P:1Sn, e.g.,         2P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to 10P:1Sn, e.g.,         3P:1Sn to 10P:1Sn, e.g., greater than 2P:1Sn to less than         10P:1Sn, e.g., 2P:1Sn to 5P:1Sn, e.g., greater than 2P:1Sn to         5P:1Sn, e.g., 3P:1Sn to 5P:1Sn, e.g., 2P:1Sn, e.g., 3P:1Sn,         e.g., 5P:1Sn. For instance, wherein the complex is formed from a         mixture comprising tin (II) fluoride and the tripolyphosphate         salt, e.g., alkali tripolyphosphate salt, in a molar ratio of         1P:1Sn to less than 15P:1Sn, e.g., greater than 1P:1Sn to less         than 15P:1Sn, e.g., 2P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to         10P:1Sn, e.g., 2P:1Sn to 5P:1Sn, e.g., 2P:1Sn, e.g., 5P:1Sn. For         instance, wherein the complex is formed from a mixture         comprising tin (II) chloride and the tripolyphosphate salt,         e.g., alkali tripolyphosphate salt, in a molar ratio of 2P:1Sn         to 10P:1Sn, e.g., 3P:1Sn to 10P:1Sn, e.g., greater than 2P:1Sn         to less than 10P:1Sn, e.g., 2P:1Sn to 5P:1Sn, e.g., greater than         2P:1Sn to 5P:1Sn, e.g., 3P:1Sn to 5P:1Sn, e.g., 3P:1Sn, e.g.,         5P:1Sn.     -   1.47 Any of the foregoing complexes, wherein the complex is         formed from a mixture comprising tin (II) fluoride or tin (II)         chloride and the tripolyphosphate salt, e.g., alkali         tripolyphosphate salt, in a molar ratio of 2P:1Sn to 5P:1Sn,         e.g., greater than 2P:1Sn to 5P:1Sn, e.g., 3P:1Sn to 5P:1Sn,         e.g., 2P:1Sn, e.g., 3P:1Sn, e.g., 5P:1Sn. For instance, wherein         the complex is formed from a mixture comprising tin (II)         fluoride and the tripolyphosphate salt, e.g., alkali         tripolyphosphate salt, in a molar ratio of 2P:1Sn to 5P:1Sn,         e.g., 2P:1Sn, e.g., 5P:1Sn. For instance, wherein the complex is         formed from a mixture comprising tin (II) chloride and the         tripolyphosphate salt, e.g., alkali tripolyphosphate salt, in a         molar ratio of greater than 2P:1Sn to 5P:1Sn, e.g., 3P:1Sn to         5P:1Sn, e.g., 3P:1Sn, e.g., 5P:1Sn.     -   1.48 Any of the foregoing complexes, wherein the complex is         formed from a mixture comprising tin (II) fluoride or tin (II)         chloride and sodium tripolyphosphate in a molar ratio of 1P:1Sn         to less than 15P:1Sn, e.g., greater than 1P:1Sn to less than         15P:1Sn, e.g., 2P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to         10P:1Sn, e.g., 3P:1Sn to 10P:1Sn, e.g., greater than 2P:1Sn to         less than 10P:1Sn, e.g., 2P:1Sn to 5P:1Sn, e.g., greater than         2P:1Sn to 5P:1Sn, e.g., 3P:1Sn to 5P:1Sn, e.g., 2P:1Sn, e.g.,         3P:1Sn, e.g., 5P:1Sn. For instance, wherein the complex is         formed from a mixture comprising tin (II) fluoride and sodium         tripolyphosphate in a molar ratio of 1P:1Sn to less than         15P:1Sn, e.g., greater than 1P:1Sn to less than 15P:1Sn, e.g.,         2P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to 10P:1Sn, e.g.,         2P:1Sn to 5P:1Sn, e.g., 2P:1Sn, e.g., 5P:1Sn. For instance,         wherein the complex is formed from a mixture comprising tin (II)         chloride and sodium tripolyphosphate in a molar ratio of 2P:1Sn         to 10P:1Sn, e.g., 3P:1Sn to 10P:1Sn, e.g., greater than 2P:1Sn         to less than 10P:1Sn, e.g., 2P:1Sn to 5P:1Sn, e.g., greater than         2P:1Sn to 5P:1Sn, e.g., 3P:1Sn to 5P:1Sn, e.g., 3P:1Sn, e.g.,         5P:1Sn.     -   1.49 Complex 1.48, wherein the complex is formed from a mixture         comprising tin (II) fluoride and sodium tripolyphosphate in a         molar ratio of 2P:1Sn to 5P:1Sn, e.g., 2P:1Sn, e.g., 5P:1Sn.     -   1.50 Complex 1.48, wherein the complex is formed from a mixture         comprising tin (II) chloride and sodium tripolyphosphate in a         molar ratio of 2P:1Sn to less than 10P:1Sn, e.g., greater than         2P:1Sn to 5P:1Sn, e.g., 3P:1Sn to 5P:1Sn, e.g., 3P:1Sn, e.g.,         5P:1Sn.     -   1.51 Any of the foregoing complexes, wherein the complex is         formed from a mixture comprising 1-10 weight % tin (II) fluoride         or tin (II) chloride by weight of the mixture, e.g., 1-9 weight         % tin (II) fluoride or tin (II) chloride by weight of the         mixture, e.g., 3 weight % tin (II) fluoride or tin (II) chloride         by weight of the mixture, e.g., 2 weight % tin (II) fluoride or         tin (II) chloride by weight of the mixture, and 1-20 weight %         tripolyphosphate salt, e.g., alkali tripolyphosphate salt, by         weight of the mixture, e.g., 1-15 weight % tripolyphosphate salt         by weight of the mixture, e.g., more than 3 weight %         tripolyphosphate salt to less than 16 weight % tripolyphosphate         salt by weight of the mixture, e.g., 4-15 weight %         tripolyphosphate salt by weight of the mixture, e.g., 1-10         weight % tripolyphosphate salt by weight of the mixture, e.g.,         4-10 weight % tripolyphosphate salt by weight of the mixture,         e.g., 3-4 weight % tripolyphosphate salt by weight of the         mixture, e.g., 7-8 weight % tripolyphosphate salt by weight of         the mixture. For instance, wherein the complex is formed from a         mixture comprising 1-10 weight % tin (II) fluoride by weight of         the mixture, e.g., 1-9 weight % tin (II) fluoride by weight of         the mixture, e.g., 2 weight % tin (II) fluoride by weight of the         mixture, and 1-10 weight % tripolyphosphate salt, e.g., alkali         tripolyphosphate salt, by weight of the mixture, e.g., 3-4         weight % tripolyphosphate salt by weight of the mixture, e.g.,         7-8 weight % tripolyphosphate salt by weight of the mixture. For         instance, wherein the complex is formed from a mixture         comprising 1-10 weight % tin (II) chloride by weight of the         mixture, e.g., 1-9 weight % tin (II) chloride by weight of the         mixture, e.g., 3 weight % tin (II) chloride by weight of the         mixture, and 1-20 weight % tripolyphosphate salt, e.g., alkali         tripolyphosphate salt, by weight of the mixture, e.g., 1-15         weight % tripolyphosphate salt by weight of the mixture, e.g.,         more than 3 weight % tripolyphosphate to less than 16 weight %         tripolyphosphate salt by weight of the mixture, e.g., 4-15         weight % tripolyphosphate salt by weight of the mixture, e.g.,         1-10 weight % tripolyphosphate salt by weight of the mixture,         e.g., 4-10 weight % tripolyphosphate salt by weight of the         mixture.     -   1.52 Any of the foregoing complexes, wherein the complex is         formed from a mixture comprising 1-10 weight % tin (II) fluoride         or tin (II) chloride by weight of the mixture, e.g., 1-9 weight         % tin (II) fluoride or tin (II) chloride by weight of the         mixture, e.g., 3 weight % tin (II) fluoride or tin (II) chloride         by weight of the mixture, e.g., 2 weight % tin (II) fluoride or         tin (II) chloride by weight of the mixture, and 1-20 weight %         sodium tripolyphosphate by weight of the mixture, e.g., 1-15         weight % sodium tripolyphosphate by weight of the mixture, e.g.,         more than 3 weight % sodium tripolyphosphate to less than 16         weight % sodium tripolyphosphate by weight of the mixture, e.g.,         4-15 weight % sodium tripolyphosphate by weight of the mixture,         e.g., 1-10 weight % sodium tripolyphosphate by weight of the         mixture, e.g., 4-10 weight % sodium tripolyphosphate by weight         of the mixture, e.g., 3-4 weight % sodium tripolyphosphate by         weight of the mixture, e.g., 7-8 weight % sodium         tripolyphosphate by weight of the mixture.     -   1.53 Any of the foregoing complexes, wherein the complex is         isolated.     -   1.54 Any of the foregoing complexes, wherein the complex is         lyophilized.     -   1.55 Any of the foregoing complexes, wherein the complex is         isolated with an anti-solvent, e.g., an organic solvent, e.g.,         ethanol.     -   1.56 Any of the foregoing complexes for use in an oral care         composition, e.g., mouthwash, oral gel, or dentifrice.     -   1.57 Any of the foregoing complexes for use to reduce or inhibit         dentinal hypersensitivity, dental caries, gingivitis, or plaque.

Further provided is a method (Method 1a) to reduce or inhibit one or more of dentinal hypersensitivity, dental caries, gingivitis, and plaque in a person in need thereof comprising administering an effective amount of any of Complex 1 et seq. to the oral cavity of the person.

Further provided is a method (Method 1b) of occluding dentin tubules in a person in need thereof comprising administering an effective amount of any of Complex 1 et seq. to the oral cavity of the person.

Further provided is a method (Method 2) of making an aqueous soluble tin phosphate complex, e.g., any of Complex 1 et seq., comprising combining tin (II) fluoride or tin (II) chloride and a tripolyphosphate salt, e.g., an alkali tripolyphosphate salt, e.g., potassium tripolyphosphate or sodium tripolyphosphate, e.g.,

-   -   2.1 Method 2 comprising combining tin (II) fluoride and the         tripolyphosphate salt, e.g., alkali tripolyphosphate salt, e.g.,         sodium tripolyphosphate, in an aqueous solution.     -   2.2 Method 2 comprising combining tin (II) chloride and the         tripolyphosphate salt, e.g., alkali tripolyphosphate salt, e.g.,         sodium tripolyphosphate, in an aqueous solution.     -   2.3 Method 2.1, wherein the aqueous solution has a pH from 4-9,         e.g., from 5-8, e.g., from 5-7, e.g., from 5-6, e.g., from 6-8,         e.g., from 6-7, e.g., from 7-8.     -   2.4 Method 2.2, wherein the aqueous solution has a pH from 4-9,         e.g., from 4-8, e.g., from 4-7, e.g., from 5-8, e.g., from 6-8,         e.g., from 5-7, e.g., from 4-6, e.g., from 4-5, e.g., from 5-6,         e.g., from 6-7, e.g., from 7-8.     -   2.5 Any of the foregoing methods comprising combining tin (II)         fluoride or tin (II) chloride and the tripolyphosphate salt,         e.g., alkali tripolyphosphate salt, in a molar ratio of 1P:1Sn         to less than 15P:1Sn, e.g., greater than 1P:1Sn to less than         15P:1Sn, e.g., 2P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to         10P:1Sn, e.g., 3P:1Sn to 10P:1Sn, e.g., greater than 2P:1Sn to         less than 10P:1Sn, e.g., 2P:1Sn to 5P:1Sn, e.g., greater than         2P:1Sn to 5P:1Sn, e.g., 3P:1Sn to 5P:1Sn, e.g., 2P:1Sn, e.g.,         3P:1Sn, e.g., 5P:1Sn. For instance, comprising combining         tin (II) fluoride and the tripolyphosphate salt, e.g., alkali         tripolyphosphate salt, in a molar ratio of 1P:1Sn to less than         15P:1Sn, e.g., greater than 1P:1Sn to less than 15P:1Sn, e.g.,         2P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to 10P:1Sn, e.g.,         2P:1Sn to 5P:1Sn, e.g., 2P:1Sn, e.g., 5P:1Sn. For instance,         comprising combining tin (II) chloride and the tripolyphosphate         salt, e.g., alkali tripolyphosphate salt, in a molar ratio of         2P:1Sn to 10P:1Sn, e.g., 3P:1Sn to 10P:1Sn, e.g., greater than         2P:1Sn to less than 10P:1Sn, e.g., 2P:1Sn to 5P:1Sn, e.g.,         greater than 2P:1Sn to 5P:1Sn, e.g., 3P:1Sn to 5P:1Sn, e.g.,         3P:1Sn, e.g., 5P:1Sn.     -   2.6 Any of the foregoing methods, wherein the tripolyphosphate         salt is sodium tripolyphosphate.     -   2.7 Any of the foregoing methods comprising combining tin (II)         fluoride or tin (II) chloride and sodium tripolyphosphate in a         molar ratio of 1P:1Sn to less than 15P:1Sn, e.g., greater than         1P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to less than 15P:1Sn,         e.g., 2P:1Sn to 10P:1Sn, e.g., 3P:1Sn to 10P:1Sn, e.g., greater         than 2P:1Sn to less than 10P:1Sn, e.g., 2P:1Sn to 5P:1Sn, e.g.,         greater than 2P:1Sn to 5P:1Sn, e.g., 3P:1Sn to 5P:1Sn, e.g.,         2P:1Sn, e.g., 3P:1Sn, e.g., 5P:1Sn. For instance, comprising         combining tin (II) fluoride and sodium tripolyphosphate in a         molar ratio of 1P:1Sn to less than 15P:1Sn, e.g., greater than         1P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to less than 15P:1Sn,         e.g., 2P:1Sn to 10P:1Sn, e.g., 2P:1Sn to 5P:1Sn, e.g., 2P:1Sn,         e.g., 5P:1Sn. For instance, comprising combining tin (II)         chloride and sodium tripolyphosphate in a molar ratio of 2P:1Sn         to 10P:1Sn, e.g., 3P:1Sn to 10P:1Sn, e.g., greater than 2P:1Sn         to less than 10P:1Sn, e.g., 2P:1Sn to 5P:1Sn, e.g., greater than         2P:1Sn to 5P:1Sn, e.g., 3P:1Sn to 5P:1Sn, e.g., 3P:1Sn, e.g.,         5P:1Sn.     -   2.8 Method 2.7 comprising combining tin (II) fluoride and sodium         tripolyphosphate in a molar ratio of 2P:1Sn to 5P:1Sn, e.g.,         2P:1Sn, e.g., 5P:1Sn.     -   2.9 Method 2.7 comprising combining tin (II) chloride and sodium         tripolyphosphate in a molar ratio of greater than 2P:1Sn to less         than 10P:1Sn, e.g., greater than 2P:1Sn to 5P:1Sn, e.g., 3P:1Sn         to 5P:1Sn, e.g., 3P:1Sn, e.g., 5P:1Sn.     -   2.10 Any of the foregoing methods comprising combining 1-10         weight % tin (II) fluoride or tin (II) chloride by weight of the         combination, e.g., 1-9 weight % tin (II) fluoride or tin (II)         chloride by weight of the combination, e.g., 3 weight % tin (II)         fluoride or tin (II) chloride by weight of the combination,         e.g., 2 weight % tin (II) fluoride or tin (II) chloride by         weight of the combination, and 1-20 weight % tripolyphosphate         salt, e.g., alkali tripolyphosphate salt by weight of the         combination, e.g., 1-15 weight % tripolyphosphate salt by weight         of the combination, e.g., more than 3 weight % tripolyphosphate         salt to less than 16 weight % tripolyphosphate salt by weight of         the combination, e.g., 4-15 weight % tripolyphosphate salt by         weight of the combination, e.g., 1-10 weight % tripolyphosphate         salt by weight of the combination, e.g., 4-10 weight %         tripolyphosphate salt by weight of the combination, e.g., 3-4         weight % tripolyphosphate salt by weight of the combination,         e.g., 7-8 weight % tripolyphosphate salt by weight of the         combination. For instance, comprising combining 1-10 weight %         tin (II) fluoride by weight of the combination, e.g., 1-9 weight         % tin (II) fluoride by weight of the combination, e.g., 2 weight         % tin (II) fluoride by weight of the combination, and 1-10         weight % tripolyphosphate salt, e.g., alkali tripolyphosphate         salt, by weight of the combination, e.g., 3-4 weight %         tripolyphosphate salt by weight of the combination, e.g., 7-8         weight % tripolyphosphate salt by weight of the combination. For         instance, comprising combining 1-10 weight % tin (II) chloride         by weight of the combination, e.g., 1-9 weight % tin (II)         chloride by weight of the combination, e.g., 3 weight % tin (II)         chloride by weight of the combination, and 1-20 weight %         tripolyphosphate salt, e.g., alkali tripolyphosphate salt, by         weight of the combination, e.g., 1-15 weight % tripolyphosphate         salt by weight of the combination, e.g., more than 3 weight %         tripolyphosphate salt to less than 16 weight % tripolyphosphate         salt by weight of the combination, e.g., 4-15 weight %         tripolyphosphate salt by weight of the combination, e.g., 1-10         weight % tripolyphosphate salt by weight of the combination,         e.g., 4-10 weight % tripolyphosphate salt by weight of the         combination.     -   2.11 Any of the foregoing methods comprising combining 1-10         weight % tin (II) fluoride or tin (II) chloride by weight of the         combination, e.g., 1-9 weight % tin (II) fluoride or tin (II)         chloride by weight of the combination, e.g., 3 weight % tin (II)         fluoride or tin (II) chloride by weight of the combination,         e.g., 2 weight % tin (II) fluoride or tin (II) chloride by         weight of the combination, and 1-20 weight % sodium         tripolyphosphate by weight of the combination, e.g., more than 3         weight % sodium tripolyphosphate to less than 16 weight % sodium         tripolyphosphate by weight of the combination, e.g., 4-15 weight         % sodium tripolyphosphate by weight of the combination, e.g.,         1-10 weight % sodium tripolyphosphate by weight of the         combination, e.g., 4-10 weight % sodium tripolyphosphate by         weight of the combination, e.g., 3-4 weight % sodium         tripolyphosphate by weight of the combination, e.g., 7-8 weight         % sodium tripolyphosphate by weight of the combination. For         instance, comprising combining 1-10 weight % tin (II) fluoride         by weight of the combination, e.g., 1-9 weight % tin (II)         fluoride by weight of the combination, e.g., 2 weight % tin (II)         fluoride by weight of the combination, and 1-10 weight % sodium         tripolyphosphate by weight of the combination, e.g., 3-4 weight         % sodium tripolyphosphate by weight of the combination, e.g.,         7-8 weight % sodium tripolyphosphate by weight of the         combination. For instance, comprising combining 1-10 weight %         tin (II) chloride by weight of the combination, e.g., 1-9 weight         % tin (II) chloride by weight of the combination, e.g., 3 weight         % tin (II) chloride by weight of the combination, and 1-20         weight % sodium tripolyphosphate by weight of the combination,         e.g., 1-15 weight % sodium tripolyphosphate by weight of the         combination, e.g., more than 3 weight % sodium tripolyphosphate         to less than 16 weight % sodium tripolyphosphate by weight of         the combination, e.g., 4-15 weight % sodium tripolyphosphate by         weight of the combination, e.g., 1-10 weight % sodium         tripolyphosphate by weight of the combination, e.g., 4-10 weight         % sodium tripolyphosphate by weight of the combination.     -   2.12 Any of the foregoing methods comprising isolating the         complex in solid form.     -   2.13 Any of the foregoing methods comprising lyophilizing the         complex.     -   2.14 Any of the foregoing methods comprising isolating the         complex with an anti-solvent, e.g., an organic solvent, e.g.,         ethanol.     -   2.15 An oral care composition, e.g., a mouthwash, oral gel, or         dentifrice, e.g., a mouthwash, comprising an aqueous soluble tin         phosphate complex made as described in any of the foregoing         methods.

Further provided is an aqueous soluble tin phosphate complex made by any of Method 2 et seq.

Further provided is an oral care composition (Composition 1) comprising an aqueous soluble tin phosphate complex formed from a mixture comprising tin (II) fluoride or tin (II) chloride and a tripolyphosphate salt, e.g., an alkali tripolyphosphate salt, e.g., potassium tripolyphosphate (K₅P₃O₁₀) or sodium tripolyphosphate (Na₅P₃O₁₀) (STPP), e.g., any of Complex 1 et seq., e.g.,

-   -   1.1 Composition 1, wherein the tripolyphosphate salt is sodium         tripolyphosphate (Na₅P₃O₁₀).     -   1.2 Composition 1 or 1.1, wherein the complex is formed in the         composition in situ, e.g., wherein the composition has a pH from         4-9, e.g., from 5-8, e.g., from 5-7, e.g., from 5-6, e.g., from         6-8, e.g., from 6-7, e.g., from 7-8. For instance, wherein the         complex is formed in situ in the composition from tin (II)         fluoride and the tripolyphosphate salt, e.g., alkali         tripolyphosphate salt, e.g., wherein the composition has a pH         from 4-9, e.g., from 5-8, e.g., from 5-7, e.g., from 5-6, e.g.,         from 6-8, e.g., from 6-7, e.g., from 7-8. For instance, wherein         the complex is formed in situ in the composition from tin (II)         chloride and the tripolyphosphate salt, e.g., alkali         tripolyphosphate salt, e.g., wherein the composition has a pH         from 4-8, e.g., from 4-7, e.g., from 5-8, e.g., from 5-7, e.g.,         from 4-6, e.g., from 4-5, e.g., from 5-6, e.g., from 6-7, e.g.,         from 7-8.     -   1.3 Any of Composition 1 or 1.1, wherein the complex is formed         in situ in an aqueous solution and combined with the         composition, e.g., wherein the aqueous solution has a pH from         4-9, e.g., from 5-8, e.g., from 5-7, e.g., from 5-6, e.g., from         6-8, e.g., from 6-7, e.g., from 7-8. For instance, wherein the         complex is formed in situ in an aqueous solution from tin (II)         fluoride and the tripolyphosphate salt, e.g., alkali         tripolyphosphate salt, e.g., wherein the aqueous solution has a         pH from 4-9, e.g., from 5-8, e.g., from 5-7, e.g., from 5-6,         e.g., from 6-8, e.g., from 6-7, e.g., from 7-8. For instance,         wherein the complex is formed in situ in an aqueous solution         from tin (II) chloride and the tripolyphosphate salt, e.g.,         alkali tripolyphosphate salt, e.g., wherein the aqueous solution         has a pH from 4-9, e.g., from 4-8, e.g., from 4-7, e.g., from         5-8, e.g., from 6-8, e.g., from 5-7, e.g., from 4-6, e.g., from         4-5, e.g., from 5-6, e.g., from 6-7, e.g., from 7-8.     -   1.4 Any of Composition 1, 1.1, or 1.3, wherein the complex is         combined as a solid with the composition, e.g., wherein the         complex is isolated from the aqueous solution in solid form and         combined with the composition.     -   1.5 Any of Composition 1, 1.1, 1.3, or 1.4, wherein the complex         is lyophilized and combined with the composition.     -   1.6 Any of Composition 1, 1.1, or 1.3-1.5, wherein the complex         is isolated with an anti-solvent, e.g., an organic solvent,         e.g., ethanol, and combined with the composition.     -   1.7 Any of the foregoing compositions, wherein the complex is         made as described in any of Method 2 et seq.     -   1.8 Any of the foregoing compositions, wherein the complex is         present in an amount of 2-30 weight % by weight of the         composition.     -   1.9 Any of the foregoing compositions, wherein the complex is         formed from tin (II) fluoride or tin (II) chloride and the         tripolyphosphate salt, e.g., alkali tripolyphosphate salt, in a         molar ratio of 1P:1Sn to less than 15P:1Sn, e.g., greater than         1P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to less than 15P:1Sn,         e.g., 2P:1Sn to 10P:1Sn, e.g., 3P:1Sn to 10P:1Sn, e.g., greater         than 2P:1Sn to less than 10P:1Sn, e.g., 2P:1Sn to 5P:1Sn, e.g.,         greater than 2P:1Sn to 5P:1Sn, e.g., 3P:1Sn to 5P:1Sn, e.g.,         2P:1Sn, e.g., 3P:1Sn, e.g., 5P:1Sn. For instance, wherein the         complex is formed from tin (II) fluoride and the         tripolyphosphate salt, e.g., alkali tripolyphosphate salt, in a         molar ratio of 1P:1Sn to less than 15P:1Sn, e.g., greater than         1P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to less than 15P:1Sn,         e.g., 2P:1Sn to 10P:1Sn, e.g., 2P:1Sn to 5P:1Sn, e.g., 2P:1Sn,         e.g., 5P:1Sn. For instance, wherein the complex is formed from         tin (II) chloride and the tripolyphosphate salt, e.g., alkali         tripolyphosphate salt, in a molar ratio of 2P:1Sn to 10P:1Sn,         e.g., 3P:1Sn to 10P:1Sn, e.g., greater than 2P:1Sn to less than         10P:1Sn, e.g., 2P:1Sn to 5P:1Sn, e.g., greater than 2P:1Sn to         5P:1Sn, e.g., 3P:1Sn to 5P:1Sn, e.g., 3P:1Sn, e.g., 5P:1Sn.     -   1.10 Any of the foregoing compositions, wherein the complex is         formed from tin (II) fluoride or tin (II) chloride and sodium         tripolyphosphate in a molar ratio of 1P:1Sn to less than         15P:1Sn, e.g., greater than 1P:1Sn to less than 15P:1Sn, e.g.,         2P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to 10P:1Sn, e.g.,         3P:1Sn to 10P:1Sn, e.g., greater than 2P:1Sn to less than         10P:1Sn, e.g., 2P:1Sn to 5P:1Sn, e.g., 3P:1Sn to 5P:1Sn, e.g.,         2P:1Sn, e.g., 3P:1Sn, e.g., 5P:1Sn. For instance, wherein the         complex is formed from tin (II) fluoride and sodium         tripolyphosphate in a molar ratio of 1P:1Sn to less than         15P:1Sn, e.g., greater than 1P:1Sn to less than 15P:1Sn, e.g.,         2P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to 10P:1Sn, e.g.,         2P:1Sn to 5P:1Sn, e.g., 2P:1Sn, e.g., 5P:1Sn. For instance,         wherein the complex is formed from tin (II) chloride and sodium         tripolyphosphate in a molar ratio of 2P:1Sn to 10P:1Sn, e.g.,         3P:1Sn to 10P:1Sn, e.g., greater than 2P:1Sn to less than         10P:1Sn, e.g., 2P:1Sn to 5P:1Sn, e.g., greater than 2P:1Sn to         5P:1Sn, e.g., 3P:1Sn to 5P:1Sn, e.g., 3P:1Sn, e.g., 5P:1Sn.     -   1.11 Composition 1.10, wherein the complex is formed from         tin (II) fluoride and sodium tripolyphosphate in a molar ratio         of 2P:1Sn to 5P:1Sn, e.g., 2P:1Sn, e.g., 5P:1Sn.     -   1.12 Composition 1.10, wherein the complex is formed from         tin (II) chloride and sodium tripolyphosphate in a molar ratio         of greater than 2P:1Sn to less than 10P:1Sn, e.g., greater than         2P:1Sn to 5P:1Sn e.g., 3P:1Sn to 5P:1Sn, e.g., 3P:1Sn, e.g.,         5P:1Sn.     -   1.13 Any of the foregoing compositions, wherein the complex is         formed from a mixture comprising 1-10 weight % tin (II) fluoride         or tin (II) chloride by weight of the mixture, e.g., 1-9 weight         % tin (II) fluoride or tin (II) chloride by weight of the         mixture, e.g., 3 weight % tin (II) fluoride or tin (II) chloride         by weight of the mixture, e.g., 2 weight % tin (II) fluoride or         tin (II) chloride by weight of the mixture, and 1-20 weight %         tripolyphosphate salt, e.g., alkali tripolyphosphate salt, by         weight of the mixture, e.g., 1-15 weight % tripolyphosphate salt         by weight of the mixture, e.g., more than 3 weight %         tripolyphosphate salt to less than 16 weight % tripolyphosphate         salt by weight of the mixture, e.g., 4-15 weight %         tripolyphosphate salt by weight of the mixture, e.g., 1-10         weight % tripolyphosphate salt by weight of the mixture, e.g.,         4-10 weight % tripolyphosphate salt by weight of the mixture,         e.g., 3-4 weight % tripolyphosphate salt by weight of the         mixture, e.g., 7-8 weight % tripolyphosphate salt by weight of         the mixture. For instance, wherein the complex is formed from a         mixture comprising 1-10 weight % tin (II) fluoride by weight of         the mixture, e.g., 1-9 weight % tin (II) fluoride by weight of         the mixture, e.g., 2 weight % tin (II) fluoride by weight of the         mixture, and 1-10 weight % tripolyphosphate salt, e.g., alkali         tripolyphosphate salt, by weight of the mixture, e.g., 3-4         weight % tripolyphosphate salt by weight of the mixture, e.g.,         7-8 weight % tripolyphosphate salt by weight of the mixture. For         instance, wherein the complex is formed from a mixture         comprising 1-10 weight % tin (II) chloride by weight of the         mixture, e.g., 1-9 weight % tin (II) chloride by weight of the         mixture, e.g., 3 weight % tin (II) chloride by weight of the         mixture, and 1-20 weight % tripolyphosphate salt, e.g., alkali         tripolyphosphate salt, by weight of the mixture, e.g., 1-15         weight % tripolyphosphate salt by weight of the mixture, e.g.,         more than 3 weight % tripolyphosphate salt to less than 16         weight % tripolyphosphate salt by weight of the mixture, e.g.,         4-15 weight % tripolyphosphate salt by weight of the mixture,         e.g., 1-10 weight % tripolyphosphate salt by weight of the         mixture, e.g., 4-10 weight % tripolyphosphate salt by weight of         the mixture.     -   1.14 Any of the foregoing compositions, wherein the complex is         formed from a mixture comprising 1-10 weight % tin (II) fluoride         or tin (II) chloride by weight of the mixture, e.g., 1-9 weight         % tin (II) fluoride or tin (II) chloride by weight of the         mixture, e.g., 3 weight % tin (II) fluoride or tin (II) chloride         by weight of the mixture, e.g., 2 weight % tin (II) fluoride or         tin (II) chloride by weight of the mixture, and 1-20 weight %         sodium tripolyphosphate by weight of the mixture, e.g., more         than 3 weight % sodium tripolyphosphate to less than 16 weight %         sodium tripolyphosphate by weight of the mixture, e.g., 4-15         weight % sodium tripolyphosphate by weight of the mixture, e.g.,         1-10 weight % sodium tripolyphosphate by weight of the mixture,         e.g., 4-10 weight % sodium tripolyphosphate by weight of the         mixture, e.g., 3-4 weight % sodium tripolyphosphate by weight of         the mixture, e.g., 7-8 weight % sodium tripolyphosphate by         weight of the mixture. For instance, wherein the complex is         formed from a mixture comprising 1-10 weight % tin (II) fluoride         by weight of the mixture, e.g., 1-9 weight % tin (II) fluoride         by weight of the mixture, e.g., 2 weight % tin (II) fluoride by         weight of the mixture, and 1-10 weight % sodium tripolyphosphate         by weight of the mixture, e.g., 3-4 weight % sodium         tripolyphosphate by weight of the mixture, e.g., 7-8 weight %         sodium tripolyphosphate by weight of the mixture. For instance,         wherein the complex is formed from a mixture comprising 1-10         weight % tin (II) chloride by weight of the mixture, e.g., 1-9         weight % tin (II) chloride by weight of the mixture, e.g., 3         weight % tin (II) chloride by weight of the mixture, and 1-20         weight % sodium tripolyphosphate by weight of the mixture, e.g.,         1-15 weight % sodium tripolyphosphate by weight of the mixture,         e.g., more than 3 weight % sodium tripolyphosphate to less than         16 weight % sodium tripolyphosphate by weight of the mixture,         e.g., 4-15 weight % tripolyphosphate salt by weight of the         mixture, e.g., 1-10 weight % tripolyphosphate salt by weight of         the mixture, e.g., 4-10 weight % tripolyphosphate salt by weight         of the mixture.     -   1.15 Any of the foregoing compositions, wherein the composition         comprises an aqueous solution.     -   1.16 Any of the foregoing compositions further comprising a         fluoride ion source, e.g., a fluoride ion source selected from         stannous fluoride, sodium fluoride, potassium fluoride, sodium         monofluorophosphate, sodium fluorosilicate, ammonium         fluorosilicate, amine fluoride (e.g.,         N′-octadecyltrimethylendiamine-N,N,N′-tris(2-ethanol)-dihydrofluoride),         ammonium fluoride, titanium fluoride, hexafluorosulfate, and         combinations thereof.     -   1.17 Composition 1.16, wherein the fluoride ion source is         present in an amount of 0.01-5 weight % by weight of the         composition, e.g., 0.01-2 weight % by weight of the composition,         e.g., 0.01-1 weight % by weight of the composition.     -   1.18 Any of the foregoing compositions further comprising         another alkali phosphate salt.     -   1.19 Composition 1.18, wherein the alkali phosphate salt is         present in an amount of 1-10 weight % by weight of the         composition.     -   1.20 Any of the foregoing compositions further comprising a         humectant, e.g., a humectant selected from glycerin, sorbitol,         propylene glycol, polyethylene glycol, xylitol, and combinations         thereof.     -   1.21 Composition 1.20, wherein the humectant is present in an         amount of 2-50 weight % by weight of the composition, e.g.,         10-40 weight % by weight of the composition, e.g., 15-30 weight         % by weight of the composition.     -   1.22 Any of the foregoing compositions further comprising a         surfactant, e.g., selected from anionic, cationic, zwitterionic,         and nonionic surfactants, and combinations thereof, e.g.,         selected from sodium lauryl sulfate, sodium ether lauryl         sulfate, cocamidopropylbetaine, a poloxamer, and combinations         thereof.     -   1.23 Composition 1.22, wherein the surfactant is present in an         amount of 1-10 weight % by weight of the composition.     -   1.24 Any of the foregoing compositions further comprising a         thickener, e.g., selected from a polysaccharide gums, e.g.,         xanthan gum and/or carrageenan, a silica thickener, a cellulosic         polymer, e.g., sodium CMC, and combinations thereof.     -   1.25 Composition 1.24, wherein the thickener is present in an         amount of 1-10 weight % by weight of the composition.     -   1.26 Any of the foregoing compositions further comprising an         abrasive, e.g., silica abrasive.     -   1.27 Composition 1.26, wherein the abrasive is present in an         amount of 10-30 weight % by weight of the composition.     -   1.28 Any of the foregoing compositions further comprising a pH         agent to adjust the pH, e.g., selected from sodium bicarbonate,         an alkali phosphate, sodium hydroxide, citric acid, sodium         citrate, and combinations thereof.     -   1.29 Composition 1.28, wherein the pH agent is present in an         amount of 0.1-10 weight % by weight of the composition, e.g.,         1-5 weight % by weight of the composition, e.g., 1-3 weight % by         weight of the composition.     -   1.30 Any of the foregoing compositions further comprising         flavoring, fragrance, and/or coloring.     -   1.31 Any of the foregoing compositions further comprising 2-90         weight % water by weight of the composition, e.g., 2-50 weight %         water by weight of the composition, e.g., 50-80 weight % water         by weight of the composition.     -   1.32 Any of the foregoing compositions comprising more than 20         weight % water by weight of the composition, e.g., at least 30         weight % water by weight of the composition, e.g., at least 40         weight % water by weight of the composition, e.g., at least 50         weight % water by weight of the composition, e.g., at least 60         weight % water by weight of the composition, e.g., at least 70         weight % water by weight of the composition.     -   1.33 Any of the foregoing compositions, wherein the composition         comprises tin (II) fluoride.     -   1.34 Any of Composition 1 or 1.1-1.32, wherein the composition         comprises tin (II) chloride.     -   1.35 Composition 1.33, wherein the composition has a pH from         4-9, e.g., from 5-8, e.g., from 5-7, e.g., from 5-6, e.g., from         6-8, e.g., from 6-7, e.g., from 7-8.     -   1.36 Composition 1.34, wherein the composition has a pH from         4-9, e.g., from 4-8, e.g., from 4-7, e.g., from 5-8, e.g., from         6-8, e.g., from 5-7, e.g., from 4-6, e.g., from 4-5, e.g., from         5-6, e.g., from 6-7, e.g., from 7-8.     -   1.37 Any of the foregoing compositions, wherein the composition         is a mouthwash, oral gel, or dentifrice, e.g., a mouthwash.     -   1.38 Any of the foregoing compositions for use to reduce or         inhibit dentinal hypersensitivity, dental caries, gingivitis, or         plaque.

Further provided is a method (Method 3a) to reduce or inhibit one or more of dentinal hypersensitivity, dental caries, gingivitis, and plaque in a person in need thereof comprising administering an effective amount of an oral care composition comprising an aqueous soluble tin phosphate complex formed from a mixture comprising tin (II) fluoride or tin (II) chloride and a tripolyphosphate salt, e.g., an alkali tripolyphosphate salt, e.g., potassium tripolyphosphate (K₅P₃O₁₀) or sodium tripolyphosphate (Na₅P₃O₁₀), e.g., any of Composition 1 et seq., to the oral cavity of the person.

Further provided is a method (Method 3b) of occluding dentin tubules in a person in need thereof comprising administering an effective amount of an oral care composition comprising an aqueous soluble tin phosphate complex formed from a mixture comprising tin (II) fluoride or tin (II) chloride and a tripolyphosphate salt, e.g., an alkali tripolyphosphate salt, e.g., potassium tripolyphosphate (K₅P₃O₁₀) or sodium tripolyphosphate (Na₅P₃O₁₀), e.g., any of Composition 1 et seq., to the oral cavity of the person.

Further provided is Method 3a and/or 3b as follows:

-   -   3.1 Method 3a or 3b, wherein the complex is any of Complex 1 et         seq.     -   3.2 Any of Method 3a, 3b, or 3.1, wherein the complex is formed         in situ in the composition, e.g., wherein the composition has a         pH from 4-9, e.g., from 5-8, e.g., from 5-7, e.g., from 5-6,         e.g., from 6-8, e.g., from 6-7, e.g., from 7-8. For instance,         wherein the complex is formed in situ in the composition from         tin (II) fluoride and the tripolyphosphate salt, e.g., alkali         tripolyphosphate salt, e.g., wherein the composition has a pH         from 4-9, e.g., from 5-8, e.g., from 5-7, e.g., from 5-6, e.g.,         from 6-8, e.g., from 6-7, e.g., from 7-8. For instance, wherein         the complex is formed in situ in the composition from tin (II)         chloride and the tripolyphosphate salt, e.g., alkali         tripolyphosphate salt, e.g., wherein the composition has a pH         from 4-9, e.g., from 4-8, e.g., from 4-7, e.g., from 5-8, e.g.,         from 6-8, e.g., from 5-7, e.g., from 4-6, e.g., from 4-5, e.g.,         from 5-6, e.g., from 6-7, e.g., from 7-8.     -   3.3 Any of Method 3a, 3b, or 3.1, wherein the complex is formed         in situ in an aqueous solution and combined with the         composition, e.g., wherein the aqueous solution has a pH from         4-9, e.g., from 5-8, e.g., from 5-7, e.g., from 5-6, e.g., from         6-8, e.g., from 6-7, e.g., from 7-8. For instance, wherein the         complex is formed in situ in an aqueous solution from tin (II)         fluoride and the tripolyphosphate salt, e.g., alkali         tripolyphosphate salt, e.g., wherein the aqueous solution has a         pH from 4-9, e.g., from 5-8, e.g., from 5-7, e.g., from 5-6,         e.g., from 6-8, e.g., from 6-7, e.g., from 7-8. For instance,         wherein the complex is formed in situ in an aqueous solution         from tin (II) chloride and the tripolyphosphate salt, e.g.,         alkali tripolyphosphate salt, e.g., wherein the aqueous solution         has a pH from 4-9, e.g., from 4-8, e.g., from 4-7, e.g., from         5-8, e.g., from 6-8, e.g., from 5-7, e.g., from 4-6, e.g., from         4-5, e.g., from 5-6, e.g., from 6-7, e.g., from 7-8.     -   3.4 Any of Method 3a, 3b, 3.1, or 3.3, wherein the complex is         combined as a solid with the composition, e.g., wherein the         complex is isolated from the aqueous solution in solid form and         combined with the composition, e.g., mouthwash.     -   3.5 Any of Method 3a, 3b, 3.1, 3.3, or 3.4, wherein the complex         is lyophilized and combined with the composition.     -   3.6 Any of Method 3a, 3b, 3.1, or 3.3-3.5, wherein the complex         is isolated with an anti-solvent, e.g., an organic solvent,         e.g., ethanol, and combined with the composition.     -   3.7 Any of the foregoing methods, wherein the complex is made as         described in any of Method 2 et seq.     -   3.8 Any of the foregoing methods, wherein the complex is present         in an amount of 2-30 weight % by weight of the composition.     -   3.9 Any of the foregoing methods, wherein the tripolyphosphate         salt is sodium tripolyphosphate (Na₅P₃O₁₀).     -   3.10 Any of the foregoing methods, wherein the complex is formed         from tin (II) fluoride or tin (II) chloride and the         tripolyphosphate salt, e.g., alkali tripolyphosphate salt, in a         molar ratio of 1P:1Sn to less than 15P:1Sn, e.g., greater than         1P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to less than 15P:1Sn,         e.g., 2P:1Sn to 10P:1Sn, e.g., 3P:1Sn to 10P:1Sn, e.g., greater         than 2P:1Sn to less than 10P:1Sn, e.g., 2P:1Sn to 5P:1Sn, e.g.,         greater than 2P:1Sn to 5P:1Sn, e.g., 3P:1Sn to 5P:1Sn, e.g.,         2P:1Sn, e.g., 3P:1Sn, e.g., 5P:1Sn. For instance, wherein the         complex is formed from tin (II) fluoride and the         tripolyphosphate salt, e.g., alkali tripolyphosphate salt, in a         molar ratio of 1P:1Sn to less than 15P:1Sn, e.g., greater than         1P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to less than 15P:1Sn,         e.g., 2P:1Sn to 10P:1Sn, e.g., 2P:1Sn to 5P:1Sn, e.g., 2P:1Sn,         e.g., 5P:1Sn. For instance, wherein the complex is formed from         tin (II) chloride and the tripolyphosphate salt, e.g., alkali         tripolyphosphate salt, in a molar ratio of 2P:1Sn to 10P:1Sn,         e.g., 3P:1Sn to 10P:1Sn, e.g., greater than 2P:1Sn to less than         10P:1Sn, e.g., 2P:1Sn to 5P:1Sn, e.g., greater than 2P:1Sn to         5P:1Sn, e.g., 3P:1Sn to 5P:1Sn, e.g., 3P:1Sn, e.g., 5P:1Sn.     -   3.11 Any of the foregoing methods, wherein the complex is formed         from tin (II) fluoride or tin (II) chloride and sodium         tripolyphosphate in a molar ratio of 1P:1Sn to less than         15P:1Sn, e.g., greater than 1P:1Sn to less than 15P:1Sn, e.g.,         2P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to 10P:1Sn, e.g.,         3P:1Sn to 10P:1Sn, e.g., greater than 2P:1Sn to less than         10P:1Sn, e.g., 2P:1Sn to 5P:1Sn, e.g., greater than 2P:1Sn to         5P:1Sn, e.g., 3P:1Sn to 5P:1Sn, e.g., 2P:1Sn, e.g., 3P:1Sn,         e.g., 5P:1Sn. For instance, wherein the complex is formed from         tin (II) fluoride and sodium tripolyphosphate in a molar ratio         of 1P:1Sn to less than 15P:1Sn, e.g., greater than 1P:1Sn to         less than 15P:1Sn, e.g., 2P:1Sn to less than 15P:1Sn, e.g.,         2P:1Sn to 10P:1Sn, e.g., 2P:1Sn to 5P:1Sn, e.g., 2P:1Sn, e.g.,         5P:1Sn. For instance, wherein the complex is formed from         tin (II) chloride and sodium tripolyphosphate in a molar ratio         of 2P:1Sn to 10P:1Sn, e.g., 3P:1Sn to 10P:1Sn, e.g., greater         than 2P:1Sn to less than 10P:1Sn, e.g., 2P:1Sn to 5P:1Sn, e.g.,         greater than 2P:1Sn to 5P:1Sn, e.g., 3P:1Sn to 5P:1Sn, e.g.,         3P:1Sn, e.g., 5P:1Sn.     -   3.12 Method 3.11, wherein the complex is formed from tin (II)         fluoride and sodium tripolyphosphate in a molar ratio of 2P:1Sn         to 5P:1Sn, e.g., 2P:1Sn, e.g., 5P:1Sn.     -   3.13 Method 3.11, wherein the complex is formed from tin (II)         chloride and sodium tripolyphosphate in a molar ratio of greater         than 2P:1Sn to 5P:1Sn, e.g., 3P:1Sn to 5P:1Sn, e.g., 3P:1Sn,         e.g., 5P:1Sn.     -   3.14 Any of the foregoing methods, wherein the complex is formed         from a mixture comprising 1-10 weight % tin (II) fluoride or         tin (II) chloride by weight of the mixture, e.g., 1-9 weight %         tin (II) fluoride or tin (II) chloride by weight of the mixture,         e.g., 3 weight % tin (II) fluoride or tin (II) chloride by         weight of the mixture, e.g., 2 weight % tin (II) fluoride or         tin (II) chloride by weight of the mixture, and 1-20 weight %         tripolyphosphate salt, e.g., alkali tripolyphosphate salt, by         weight of the mixture, e.g., 1-15 weight % tripolyphosphate salt         by weight of the mixture, e.g., more than 3 weight %         tripolyphosphate salt to less than 16 weight % tripolyphosphate         salt by weight of the mixture, e.g., 4-15 weight %         tripolyphosphate salt by weight of the mixture, e.g., 1-10         weight % tripolyphosphate salt by weight of the mixture, e.g.,         4-10 weight % tripolyphosphate salt by weight of the mixture,         e.g., 3-4 weight % tripolyphosphate salt by weight of the         mixture, e.g., 7-8 weight % tripolyphosphate salt by weight of         the mixture. For instance, wherein the complex is formed from a         mixture comprising 1-10 weight % tin (II) fluoride by weight of         the mixture, e.g., 1-9 weight % tin (II) fluoride by weight of         the mixture, e.g., 2 weight % tin (II) fluoride by weight of the         mixture, and 1-10 weight % tripolyphosphate salt, e.g., alkali         tripolyphosphate salt, by weight of the mixture, e.g., 3-4         weight % tripolyphosphate salt by weight of the mixture, e.g.,         7-8 weight % tripolyphosphate salt by weight of the mixture. For         instance, wherein the complex is formed from a mixture         comprising 1-10 weight % tin (II) chloride by weight of the         mixture, e.g., 1-9 weight % tin (II) chloride by weight of the         mixture, e.g., 3 weight % tin (II) chloride by weight of the         mixture, and 1-20 weight % tripolyphosphate salt, e.g., alkali         tripolyphosphate salt, by weight of the mixture, e.g., 1-15         weight % tripolyphosphate salt by weight of the mixture, e.g.,         more than 3 weight % tripolyphosphate salt to less than 16         weight % tripolyphosphate salt by weight of the mixture, e.g.,         4-15 weight % tripolyphosphate salt by weight of the mixture,         e.g., 1-10 weight % tripolyphosphate salt by weight of the         mixture, e.g., 4-10 weight % tripolyphosphate salt by weight of         the mixture.     -   3.15 Any of the foregoing methods, wherein the complex is formed         from a mixture comprising 1-10 weight % tin (II) fluoride or         tin (II) chloride by weight of the mixture, e.g., 1-9 weight %         tin (II) fluoride or tin (II) chloride by weight of the mixture,         e.g., 3 weight % tin (II) fluoride or tin (II) chloride by         weight of the mixture, e.g., 2 weight % tin (II) fluoride or         tin (II) chloride by weight of the mixture, and 1-20 weight %         sodium tripolyphosphate by weight of the mixture, e.g., and 1-15         weight % sodium tripolyphosphate by weight of the mixture, e.g.,         more than 3 weight % sodium tripolyphosphate to less than 16         weight % sodium tripolyphosphate by weight of the mixture, e.g.,         4-15 weight % sodium tripolyphopshate by weight of the mixture,         e.g., 1-10 weight % sodium tripolyphosphate by weight of the         mixture, e.g., 4-10 weight % sodium tripolyphopshate by weight         of the mixture, e.g., 3-4 weight % sodium tripolyphosphate by         weight of the mixture, e.g., 7-8 weight % sodium         tripolyphosphate by weight of the mixture. For instance, wherein         the complex is formed from a mixture comprising 1-10 weight %         tin (II) fluoride by weight of the mixture, e.g., 1-9 weight %         tin (II) fluoride by weight of the mixture, e.g., 2 weight %         tin (II) fluoride by weight of the mixture, and 1-10 weight %         sodium tripolyphosphate by weight of the mixture, e.g., 3-4         weight % sodium tripolyphosphate by weight of the mixture, e.g.,         7-8 weight % sodium tripolyphosphate by weight of the mixture.         For instance, wherein the complex is formed from a mixture         comprising 1-10 weight % tin (II) chloride by weight of the         mixture, e.g., 1-9 weight % tin (II) chloride by weight of the         mixture, e.g., 3 weight % tin (II) chloride by weight of the         mixture, and 1-20 weight % sodium tripolyphosphate by weight of         the mixture, e.g., 1-15 weight % sodium tripolyphosphate by         weight of the mixture, e.g., more than 3 weight % sodium         tripolyphosphate to less than 16 weight % sodium         tripolyphosphate by weight of the mixture, e.g., 4-15 weight %         sodium tripolyphosphate by weight of the mixture, e.g., 1-10         weight % sodium tripolyphosphate by weight of the mixture, e.g.,         4-10 weight % sodium tripolyphosphate by weight of the mixture.     -   3.16 Any of the foregoing methods, wherein the composition         further comprises a fluoride ion source, e.g., a fluoride ion         source selected from stannous fluoride, sodium fluoride,         potassium fluoride, sodium monofluorophosphate, sodium         fluorosilicate, ammonium fluorosilicate, amine fluoride (e.g.,         N′-octadecyltrimethylendiamine-N,N,N′-tris(2-ethanol)-dihydrofluoride),         ammonium fluoride, titanium fluoride, hexafluorosulfate, and         combinations thereof.     -   3.17 Method 3.16, wherein the fluoride ion source is present in         an amount of 0.01-5 weight % by weight of the composition, e.g.,         0.01-2 weight % by weight of the composition, e.g., 0.01-1         weight % by weight of the composition.     -   3.18 Any of the foregoing methods, wherein the composition         further comprises another alkali phosphate salt.     -   3.19 Method 3.18, wherein the alkali phosphate salt is present         in an amount of 1-10 weight % by weight of the composition.     -   3.20 Any of the foregoing methods, wherein the composition         further comprises a humectant, e.g., a humectant selected from         glycerin, sorbitol, propylene glycol, polyethylene glycol,         xylitol, and combinations thereof.     -   3.21 Method 3.20, wherein the humectant is present in an amount         of 2-50 weight % by weight of the composition, e.g., 10-40         weight % by weight of the composition, e.g., 15-30 weight % by         weight of the composition.     -   3.22 Any of the foregoing methods, wherein the composition         further comprises a surfactant, e.g., selected from anionic,         cationic, zwitterionic, and nonionic surfactants, and         combinations thereof, e.g., selected from sodium lauryl sulfate,         sodium ether lauryl sulfate, cocamidopropylbetaine, a poloxamer,         and combinations thereof.     -   3.23 Method 3.22, wherein the surfactant is present in an amount         of 1-10 weight % by weight of the composition.     -   3.24 Any of the foregoing methods, wherein the composition         further comprises a thickener, e.g., selected from a         polysaccharide gums, e.g., xanthan gum and/or carrageenan, a         silica thickener, a cellulosic polymer, e.g., sodium CMC, and         combinations thereof.     -   3.25 Method 3.24, wherein the thickener is present in an amount         of 1-10 weight % by weight of the composition.     -   3.26 Any of the foregoing methods, wherein the composition         further comprises an abrasive, e.g., silica abrasive.     -   3.27 Method 3.26, wherein the abrasive is present in an amount         of 10-30 weight % by weight of the composition.     -   3.28 Any of the foregoing methods, wherein the composition         further comprises a pH agent to adjust the pH, e.g., selected         from sodium bicarbonate, an alkali phosphate, sodium hydroxide,         citric acid, sodium citrate, and combinations thereof.     -   3.29 Method 3.28, wherein the pH agent is present in an amount         of 0.1-10 weight % by weight of the composition, e.g., 1-5         weight % by weight of the composition, e.g., 1-3 weight % by         weight of the composition.     -   3.30 Any of the foregoing methods, wherein the composition         further comprises flavoring, fragrance, and/or coloring.     -   3.31 Any of the foregoing methods, wherein the composition         further comprises 2-90 weight % water by weight of the         composition, e.g., 2-50 weight % water by weight of the         composition, e.g., 50-80 weight % water by weight of the         composition.     -   3.32 Any of the foregoing methods, wherein the composition         further comprises more than 20 weight % water by weight of the         composition, e.g., at least 30 weight % water by weight of the         composition, e.g., at least 40 weight % water by weight of the         composition, e.g., at least 50 weight % water by weight of the         composition, e.g., at least 60 weight % water by weight of the         composition, e.g., at least 70 weight % water by weight of the         composition.     -   3.33 Any of the foregoing methods, wherein the composition         comprises an aqueous solution.     -   3.34 Any of the foregoing methods, wherein the composition         comprises tin (II) fluoride.     -   3.35 Any of Method 3a, 3b, or 3.1-3.33, wherein the composition         comprises tin (II) chloride.     -   3.36 Method 3.34, wherein the composition has a pH from 4-9,         e.g. from 5-8, e.g., from 5-7, e.g., from 5-6, e.g., from 6-8,         e.g., from 6-7, e.g., from 7-8.     -   3.37 Method 3.35, wherein the composition has a pH from 4-9,         e.g., from 4-8, e.g., from 4-7, e.g., from 5-8, e.g., from 6-8,         e.g., from 5-7, e.g., from 4-6, e.g., from 4-5, e.g., from 5-6,         e.g., from 6-7, e.g., from 7-8.     -   3.38 Any of the foregoing methods, wherein the composition is         any of Composition 1 et seq.     -   3.39 Any of the foregoing methods, wherein the composition is a         mouthwash, oral gel, or dentifrice, e.g., a mouthwash.     -   3.40 Any of the foregoing methods to reduce or inhibit dentinal         hypersensitivity.     -   3.41 Any of the foregoing methods to reduce or inhibit dental         caries.     -   3.42 Any of the foregoing methods to reduce or inhibit         gingivitis.     -   3.43 Any of the foregoing methods to reduce or inhibit plaque.     -   3.44 Any of the foregoing methods to occlude dentin tubules.

Further provided is a method (Method 4) of making an oral care composition, e.g., any of Composition 1 et seq., comprising an aqueous soluble tin phosphate complex formed from a mixture comprising tin (II) fluoride or tin (II) chloride and a tripolyphosphate salt, e.g., an alkali tripolyphosphate salt, e.g., potassium tripolyphosphate (K₅P₃O₁₀) or sodium tripolyphosphate (Na₅P₃O₁₀), e.g., any of Complex 1 et seq., comprising combining the complex, e.g., any of Complex 1 et seq., with an oral care base, e.g., a mouthwash, oral gel, or dentifrice base, e.g.,

-   -   4.1 Method 4, wherein the complex is formed in situ in the         composition, e.g., wherein the composition has a pH from 4-9,         e.g., from 5-8, e.g., from 5-7, e.g., from 5-6, e.g., from 6-8,         e.g., from 6-7, e.g., from 7-8. For instance, wherein the         complex is formed in situ in the composition from tin (II)         fluoride and the tripolyphosphate salt, e.g., alkali         tripolyphosphate salt, e.g., wherein the composition has a pH         from 4-9, e.g., from 5-8, e.g., from 5-7, e.g., from 5-6, e.g.,         from 6-8, e.g., from 6-7, e.g., from 7-8. For instance, wherein         the complex is formed in situ in the composition from tin (II)         chloride and the tripolyphosphate salt, e.g., alkali         tripolyphosphate salt, e.g., wherein the composition has a pH         from 4-9, e.g., from 4-8, e.g., from 4-7, e.g., from 5-8, e.g.,         from 6-8, e.g., from 5-7, e.g., from 4-6, e.g., from 4-5, e.g.,         from 5-6, e.g., from 6-7, e.g., from 7-8.     -   4.2 Method 4, wherein the complex is formed in situ in an         aqueous solution and combined with the oral care base, e.g.,         wherein the aqueous solution has a pH from 4-9, e.g., from 5-8,         e.g., from 5-7, e.g., from 5-6, e.g., from 6-8, e.g., from 6-7,         e.g., from 7-8. For instance, wherein the complex is formed in         situ in an aqueous solution from tin (II) fluoride and the         tripolyphosphate salt, e.g., alkali tripolyphosphate salt, e.g.,         wherein the aqueous solution has a pH from 4-9, e.g., from 5-8,         e.g., from 5-7, e.g., from 5-6, e.g., from 6-8, e.g., from 6-7,         e.g., from 7-8. For instance, wherein the complex is formed in         situ in an aqueous solution from tin (II) chloride and the         tripolyphosphate salt, e.g., alkali tripolyphosphate salt, e.g.,         wherein the aqueous solution has a pH from 4-9, e.g., from 4-8,         e.g., from 4-7, e.g., from 5-8, e.g., from 6-8, e.g., from 5-7,         e.g., from 4-6, e.g., from 4-5, e.g., from 5-6, e.g., from 6-7,         e.g., from 7-8.     -   4.3 Method 4 or 4.2, wherein the complex is combined as a solid         with the oral care base, e.g., wherein the complex is isolated         from the aqueous solution in solid form and combined with the         oral care base, e.g., mouthwash, oral gel, or dentifrice base,         e.g., a mouthwash base.     -   4.4 Any of Method 4, 4.2, or 4.3, wherein the complex is         lyophilized and combined the complex with an oral care base,         e.g., mouthwash, oral gel, or dentifrice base, e.g., a mouthwash         base.     -   4.5 Any of Method 4 or 4.2-4.4, wherein the complex is isolated         with an anti-solvent, e.g., an organic solvent, e.g., ethanol,         and combined with the oral care base, e.g., mouthwash, oral gel,         or dentifrice base, e.g., a mouthwash base.     -   4.6 Any of the foregoing methods, wherein the complex is made as         described in any of Method 2 et seq.     -   4.7 Any of the foregoing methods, wherein the complex is present         in an amount of 2-30 weight % by weight of the composition 4.8         Any of the foregoing methods, wherein the tripolyphosphate salt         is sodium tripolyphosphate.     -   4.9 Any of the foregoing methods, wherein the complex is made by         mixing tin (II) fluoride or tin (II) chloride and the         tripolyphosphate salt, e.g., alkali tripolyphosphate salt, in a         molar ratio of 1P:1Sn to less than 15P:1Sn, e.g., greater than         1P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to less than 15P:1Sn,         e.g., 2P:1Sn to 10P:1Sn, e.g., 3P:1Sn to 10P:1Sn, e.g., greater         than 2P:1Sn to less than 10P:1Sn, e.g., 2P:1Sn to 5P:1Sn, e.g.,         greater than 2P:1Sn to 5P:1Sn, e.g., 3P:1Sn to 5P:1Sn, e.g.,         2P:1Sn, e.g., 3P:1Sn, e.g., 5P:1Sn. For instance, comprising         mixing tin (II) fluoride and the tripolyphosphate salt, e.g.,         alkali tripolyphosphate salt, in a molar ratio of 1P:1Sn to less         than 15P:1Sn, e.g., greater than 1P:1Sn to less than 15P:1Sn,         e.g., 2P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to 10P:1Sn,         e.g., 2P:1Sn to 5P:1Sn, e.g., 2P:1Sn, e.g., 5P:1Sn. For         instance, comprising mixing tin (II) chloride and the         tripolyphosphate salt, e.g., alkali tripolyphosphate salt, in a         molar ratio of 2P:1Sn to 10P:1Sn, e.g., 3P:1Sn to 10P:1Sn, e.g.,         greater than 2P:1Sn to less than 10P:1Sn, e.g., 2P:1Sn to         5P:1Sn, e.g., greater than 2P:1Sn to 5P:1Sn, e.g., 3P:1Sn to         5P:1Sn, e.g., 3P:1Sn, e.g., 5P:1Sn.     -   4.10 Any of the foregoing methods, wherein the complex is made         by mixing tin (II) fluoride or tin (II) chloride and sodium         tripolyphosphate in a molar ratio of 1P:1Sn to less than         15P:1Sn, e.g., greater than 1P:1Sn to less than 15P:1Sn, e.g.,         2P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to 10P:1Sn, e.g.,         3P:1Sn to 10P:1Sn, e.g., greater than 2P:1Sn to less than         10P:1Sn, e.g., 2P:1Sn to 5P:1Sn, e.g., greater than 2P:1Sn to         5P:1Sn, e.g., 3P:1Sn to 5P:1Sn, e.g., 2P:1Sn, e.g., 3P:1Sn,         e.g., 5P:1Sn. For instance, comprising mixing tin (II) fluoride         and sodium tripolyphosphate in a molar ratio of 1P:1Sn to less         than 15P:1Sn, e.g., greater than 1P:1Sn to less than 15P:1Sn,         e.g., 2P:1Sn to less than 15P:1Sn, e.g., 2P:1Sn to 10P:1Sn,         e.g., 2P:1Sn to 5P:1Sn, e.g., 2P:1Sn, e.g., 5P:1Sn. For         instance, comprising mixing tin (II) chloride and sodium         tripolyphosphate in a molar ratio of 2P:1Sn to 10P:1Sn, e.g.,         3P:1Sn to 10P:1Sn, e.g., greater than 2P:1Sn to less than         10P:1Sn, e.g., 2P:1Sn to 5P:1Sn, e.g., greater than 2P:1Sn to         5P:1Sn, e.g., 3P:1Sn to 5P:1Sn, e.g., 3P:1Sn, e.g., 5P:1Sn.     -   4.11 Method 4.10, wherein the complex is made by mixing tin (II)         fluoride and sodium tripolyphosphate in a molar ratio of 2P:1Sn         to 5P:1Sn, e.g., 2P:1Sn, e.g., 5P:1Sn.     -   4.12 Method 4.10, wherein the complex is made by mixing tin (II)         chloride and sodium tripolyphosphate in a molar ratio of greater         than 2P:1Sn to 5P:1Sn, e.g., 3P:1Sn to 5P:1Sn, e.g., 3P:1Sn,         e.g., 5P:1Sn.     -   4.13 Any of the foregoing methods, wherein the complex is made         by mixing 1-10 weight % tin (II) fluoride or tin (II) chloride         by weight of the mixture, e.g., 1-9 weight % tin (II) fluoride         or tin (II) chloride by weight of the mixture, e.g., 3 weight %         tin (II) fluoride or tin (II) chloride by weight of the mixture,         e.g., 2 weight % tin (II) fluoride or tin (II) chloride by         weight of the mixture, and 1-20 weight % tripolyphosphate salt,         e.g., alkali tripolyphosphate salt, by weight of the mixture,         e.g., 1-15 weight % tripolyphosphate salt by weight of the         mixture, e.g., more than 3 weight % tripolyphosphate salt to         less than 16 weight % tripolyphosphate salt by weight of the         mixture, e.g., 4-15 weight % tripolyphosphate salt by weight of         the mixture, e.g., 1-10 weight % tripolyphosphate salt by weight         of the mixture, e.g., 4-10 weight % tripolyphosphate salt by         weight of the mixture, e.g., 3-4 weight % tripolyphosphate salt         by weight of the mixture, e.g., 7-8 weight % tripolyphosphate         salt by weight of the mixture. For instance, comprising mixing         1-10 weight % tin (II) fluoride by weight of the mixture, e.g.,         1-9 weight % tin (II) fluoride by weight of the mixture, e.g., 2         weight % tin (II) fluoride by weight of the mixture, and 1-10         weight % tripolyphosphate salt, e.g., alkali tripolyphosphate         salt, by weight of the mixture, e.g., 3-4 weight %         tripolyphosphate salt by weight of the mixture, e.g., 7-8 weight         % tripolyphosphate salt by weight of the mixture. For instance,         comprising mixing 1-10 weight % tin (II) chloride by weight of         the mixture, e.g., 1-9 weight % tin (II) chloride by weight of         the mixture, e.g., 3 weight % tin (II) chloride by weight of the         mixture, and 1-20 weight % tripolyphosphate salt, e.g., alkali         tripolyphosphate salt, by weight of the mixture, e.g., 1-15         weight % tripolyphosphate salt by weight of the mixture, e.g.,         more than 3 weight % tripolyphosphate salt to less than 16         weight % tripolyphosphate salt by weight of the mixture, e.g.,         4-15 weight % tripolyphosphate salt by weight of the mixture,         e.g., 1-10 weight % tripolyphosphate salt by weight of the         mixture, e.g., 4-10 weight % tripolyphosphate salt by weight of         the mixture.     -   4.14 Any of the foregoing methods, wherein the complex is made         by mixing 1-10 weight % tin (II) fluoride or tin (II) chloride         by weight of the mixture, e.g., 1-9 weight % tin (II) fluoride         or tin (II) chloride by weight of the mixture, e.g., 3 weight %         tin (II) fluoride or tin (II) chloride by weight of the mixture,         e.g., 2 weight % tin (II) fluoride or tin (II) chloride by         weight of the mixture, and 1-20 weight % sodium tripolyphosphte         by weight of the mixture, e.g., 1-15 weight % sodium         tripolyphosphte by weight of the mixture, e.g., more than 3         weight % sodium tripolyphosphate to less than 16 weight % sodium         tripolyphosphate by weight of the mixture, e.g., 4-15 weight %         sodium tripolyphosphate by weight of the mixture, e.g., 1-10         weight % sodium tripolyphosphate by weight of the mixture, e.g.,         4-10 weight % sodium tripolyphosphate by weight of the mixture,         e.g., 3-4 weight % sodium tripolyphosphate by weight of the         mixture, e.g., 7-8 weight % sodium tripolyphosphate by weight of         the mixture. For instance, comprising mixing 1-10 weight %         tin (II) fluoride by weight of the mixture, e.g., 1-9 weight %         tin (II) fluoride by weight of the mixture, e.g., 2 weight %         tin (II) fluoride by weight of the mixture, and 1-10 weight %         sodium tripolyphosphate by weight of the mixture, e.g., 3-4         weight % sodium tripolyphosphate by weight of the mixture, e.g.,         7-8 weight % sodium tripolyphosphate by weight of the mixture.         For instance, comprising mixing 1-10 weight % tin (II) chloride         by weight of the mixture, e.g., 1-9 weight % tin (II) chloride         by weight of the mixture, e.g., 3 weight % tin (II) chloride by         weight of the mixture, and 1-20 weight % sodium tripolyphosphate         by weight of the mixture, e.g., 1-15 weight % sodium         tripolyphosphate by weight of the mixture, e.g., more than 3         weight % sodium tripolyphosphate to less than 16 weight % sodium         tripolyphosphate by weight of the mixture, e.g., 4-15 weight %         sodium tripolyphosphate salt by weight of the mixture, e.g.,         1-10 weight % sodium tripolyphosphate by weight of the mixture,         e.g., 4-10 weight % sodium tripolyphosphate salt by weight of         the mixture.     -   4.15 Any of the foregoing methods, wherein the oral care base is         a mouthwash base.

Tin (II) fluoride or tin (II) chloride and a tripolyphosphate salt, e.g., an alkali tripolyphosphate salt, e.g., sodium tripolyphosphate, may be combined to form a pre-formed aqueous soluble tin phosphate complex, e.g., any of Complex 1 et seq., which may be prepared in bulk, and then incorporated into the oral care compositions disclosed herein, e.g., any of Composition 1 et seq. Alternatively, tin (II) fluoride or tin (II) chloride and a tripolyphosphate salt, e.g., an alkali tripolyphosphate salt, e.g., sodium tripolyphosphate, may be combined during the manufacture of the oral care compositions disclosed herein, e.g., any of Composition 1 et seq., to form the complex in situ in the composition.

In some embodiments the oral care compositions disclosed herein, e.g., any of Composition 1 et seq., comprise one or more fluoride ion sources—i.e., a fluoride-containing compound having a beneficial effect on the care and hygiene of the oral cavity, for example, diminution of enamel solubility in acid and protection of the teeth against decay. Any suitable fluoride source may be employed including, without limitation, sodium fluoride, stannous fluoride, potassium fluoride, potassium stannous fluoride (SNFZ-KF), potassium fluorozirconate, sodium hexafluorostannate, stannous chlorofluoride, sodium monofluorophosphate (MFP), or a combination of two or more thereof. Where present, the fluoride source may provide fluoride ion in amounts sufficient to supply 25-25,000 ppm of fluoride ions, generally at least 500 ppm, e.g., 500-2000 ppm, e.g., 1000-1600 ppm, e.g., 1450 ppm. The appropriate level of fluoride will depend on the particular application. A toothpaste for general consumer use would typically have 1000-1500 ppm, e.g., 1100 ppm, e.g., 1000 ppm, with pediatric toothpaste having somewhat less. A dentifrice or coating for professional application could have as much as 5,000 or even 25,000 ppm fluoride. In some embodiments, the one or more further fluoride ion sources are present in the oral care compositions disclosed herein, e.g., Composition 1 et seq., in an amount of 0.01-5 weight % by weight of the composition, e.g., 0.01-2 weight % by weight of the composition, e.g., 0.01-1 weight % by weight of the composition.

In some embodiments, the oral care compositions disclosed herein, e.g., any of Composition 1 et seq., comprise one or more humectants. Any suitable humectant may be employed including, without limitation, polyhydric alcohols (polyols) such as propylene glycol, glycerin, sorbitol, xylitol, low molecular weight polyethylene glycols (PEGs), or a combination of two or more thereof. Humectants may, for example, prevent hardening of paste or gel compositions upon exposure to air. Certain humectants may also impart desirable sweetness of flavor to the compositions. In some embodiments, the one or more humectants are present in the oral care compositions disclosed herein, e.g., any of Composition 1 et seq., in an amount of 2-50 weight % by weight of the composition, e.g., 10-40 weight % by weight of the composition, e.g., 15-30 weight % by weight of the composition.

In some embodiments, the oral care compositions disclosed herein, e.g., any of Composition 1 et seq., comprise one or more surfactants. Any suitable surfactant may be employed including, without limitation, anionic, nonionic, and amphoteric surfactants. Surfactants may, for example, provide enhanced stability of the composition, to help in cleaning the oral cavity surfaces through detergency, and to increase foaming of the composition upon agitation, e.g., during brushing. Suitable anionic surfactants include, for example, water-soluble salts of C₈₋₂₀ alkyl sulfates, sulfonated monoglycerides of C₈₋₂₀ fatty acids, sarcosinates, taurates, or a combination of two or more thereof; for example sodium lauryl sulfate, sodium coconut monoglyceride sulfonate, sodium lauroyl sarcosinate, sodium lauroyl isoethionate, sodium laureth carboxylate, sodium dodecyl benzenesulfonate, or a combination of two or more thereof. In some embodiments, the one or more surfactants are present in the oral care compositions disclosed herein, e.g., Composition 1 et seq., in an amount of 1-10 weight % by weight of the composition.

In some embodiments, the oral care compositions disclosed herein, e.g., any of Composition 1 et seq., comprise one or more thickeners, which may impart a desired consistency and/or mouth feel to the composition. Any suitable thickener or binder may be employed including, without limitation, carbomers (also known as carboxyvinyl polymers), carrageenans (also known as Irish moss and more particularly 1-carrageenan (iota-carrageenan)), cellulosic polymers such as hydroxyethylcellulose, carboxymethylcellulose (CMC) and salts thereof, e.g., sodium CMC, natural gums such as gum karaya, xanthan gum, gum arabic, and gum tragacanth, inorganic thickeners such as colloidal magnesium aluminum silicate, colloidal silica, and the like, or a combination of two or more thereof. In some embodiments, the one or more thickeners are present in the oral care compositions disclosed herein, e.g., Composition 1 et seq., in an amount of 1-10 weight % by weight of the composition.

In some embodiments, the oral care compositions disclosed herein, e.g., any of Composition 1 et seq., comprise one or more flavorings. Any suitable flavoring, e.g., sweetening agent, may be employed including, without limitation, flavoring oils (e.g. oil of spearmint, peppermint, wintergreen, clove, sage, eucalyptus, marjoram, cinnamon, lemon, and orange), sucrose, sucralose, lactose, maltose, xylitol, stevia, sodium cyclamate, perillartine, aspartame, liquorice, saccharin or a salt thereof, or a combination of two or more thereof. In some embodiments, the one or more flavorings are present in the oral care compositions disclosed herein, e.g., any of Composition 1 et seq., in an amount of 0.01-10 weight % by weight of the composition, e.g., 0.05-5 weight % by weight of the composition, e.g., 0.05-0.2 weight % by weight of the composition, e.g., 1-3 weight % by weight of the composition.

In some embodiments, the oral care compositions disclosed herein, e.g., any of Composition 1 et seq., comprise one or more colorants. Any suitable colorant may be employed including, without limitation, zinc oxide, talc, titanium dioxide, pigments, dyes, or a combination of two or more thereof. In some embodiments, the colorant is a water soluble oral grade dye or colorant, including naturally-derived dyes (e.g., chlorophyll). In some embodiments, the oral care compositions disclosed herein, e.g., any of Composition 1 et seq., comprise the one or more colorants, in an amount of 0.01-5 weight % by weight of the composition, e.g., 0.05-2 weight % by weight of the composition.

In some embodiments, the oral care compositions disclosed herein, e.g., any of Composition 1 et seq., comprise water. Water employed in the preparation of commercial oral care compositions should be deionized and free of organic impurities. In some embodiments, water makes up the balance of the oral care compositions. In some embodiments, the oral care compositions disclosed herein, e.g., any of Composition 1 et seq., comprise water in an amount of 2-90 weight % by weight of the composition, e.g., 2-50 weight % by weight of the composition, e.g., 50-80 weight % by weight of the composition.

A complex disclosed herein may be described by reference to a spectrum as “substantially” shown or depicted in a figure or by one or more data points. It will be appreciated that a Fourier transform infrared, Raman, or NMR spectrum of a given sample may vary depending on factors known to those of skill in the art, e.g., instrument used, etc. Therefore, the Fourier transform infrared, Raman, and NMR spectrum peaks set forth herein will have an acceptable level of deviation. For example, for Fourier transform infrared spectra, the peaks may have an acceptable deviation of, e.g., +20 cm⁻¹ or +16 cm⁻¹ or +4 cm⁻¹ or +2 cm⁻¹ or +1 cm⁻¹ or +0.5 cm⁻¹. For example, for Raman spectra, the peaks may have an acceptable deviation of, e.g., +1-2 cm⁻¹, e.g., +1 cm⁻¹, e.g., +2 cm⁻¹. For example, for NMR spectra, the peaks may have an acceptable deviation of, e.g., +1 ppm.

As used herein, “aqueous solution” means a solution in which the solvent is water.

As used herein, “aqueous soluble tin phosphate complex” includes a complex in which 1 gram of the complex is soluble in 1 or 10 to 100 ml water, e.g., 1 or 10 to 90 ml water, e.g., 1 or 10 to 80 ml water, e.g., 1 or 10 to 70 ml water, e.g., 1 or 10 to 60 ml water, e.g., 1 or 10 to 50 ml water, e.g., 1 or 10 to 40 ml water, e.g., 1 or 10 to 30 ml water, e.g., 1 or 10 to 20 ml water, e.g., 1-10 ml water, e.g., less than 1 ml water.

EXAMPLES Example 1

TABLE 1 Solution Preparation Percent in pH Upon P:Sn Molar Ratio Amount (g) Solution Preparation 0.2 0.4 SnF₂ 2% SnF2 5.8 0.4 15% STPP 2% STPP solution 18.8 H₂O 96% H₂O 1 0.2 SnF₂  2% 4.9 0.1 STPP  2% 7.6 H₂O 96% 2 0.5 SnF₂  2% 5.6 0.7 STPP  3% 22.3 H₂O 95% 5 0.3 SnF₂  2% 7.8 1.2 STPP  8% 14.1 H₂O 90% 10 0.3 SnF₂  2% 8.0 2.5 STPP 16% 12.9 H₂O 82% 15 0.2 SnF₂  2% Does not form a 1.8 STPP 24% clear solution upon 5.8 H₂O 74% preparation

Solutions are prepared by first dissolving sodium tripolyphosphate (STPP) in water (mixing under high heat if necessary) and then adding stannous fluoride (SnF₂) to the clear solution. The solutions are then further mixed at room temperature until a clear solution forms. All of the solutions contain 2% SnF₂. A clear solution forms for all of the solutions except for P:Sn=15 molar ratio.

The solutions with a P:Sn molar ratio spanning from 1 to 15 containing 2% SnF2 are aged overnight at room temperature. After overnight aging, only the solutions with a P:Sn molar ratio spanning from 2 to 10 remain clear.

After aging for two days, the solution with a P:Sn molar ratio of 10 contains a little precipitate on the bottom of the vial.

The solutions with a P:Sn molar ratio of 2 and 5 remain stable after aging for two weeks at room temperature.

A different set of solutions with a P:Sn molar ratio of 2 and 5 are placed in a 50° C. oven for eight weeks. After the aging period, the solutions appear clear.

A 2% stannous fluoride solution shows precipitate almost immediately after dissolution.

Example 2

TABLE 2 Preparation of 1% Bovine Serum Albumin (BSA) Solutions Sample Amount of BSA (g) Amount of Total Solution (g) 1% BSA in 1Sn:2P 0.05 5 solution RT 1% BSA in 1Sn:5P 0.05 5 solution RT 1% BSA in 1Sn:2P 0.05 5 solution 37° C. 1% BSA in 1Sn:5P 0.05 5 solution 37° C. Control:1% BSA 0.02 2 in DI water

Bovine serum albumin (BSA) is used to model interaction of solutions with oral proteins.

Aging of the BSA Solutions

The solutions with a P:Sn molar ratio of 2 and 5 containing 1% bovine serum albumin (BSA) are aged at 37° C. and at room temperature overnight.

Both solutions of stannous fluoride (SnF₂) and sodium tripolyphosphate (STPP) with 1% BSA form a precipitate after aging overnight at 37° C. The solution with a P:Sn molar ratio of 5 forms clumps of precipitates. The solution with a P:Sn molar ratio of 2 appears turbid throughout.

The solution with a P:Sn molar ratio of 2 with 1% BSA forms a precipitate after aging overnight at room temperature.

The solution with a P:Sn molar ratio of 5 with 1% BSA has a little precipitate after aging overnight at room temperature but still remains relatively clear.

A 1% BSA control after aging overnight at room temperature shows no precipitate. A 1% BSA control after aging overnight at 37° C. shows no precipitate.

Bovine serum albumin (BSA) stimulates proteins found in saliva. Formation of precipitate upon exposure to BSA may block dentin tubules to provide hypersensitivity relief.

Example 3

Compositions comprising elevated concentrations of a complex comprising tin (II) fluoride and a polyphosphate, having a P:Sn molar ratio of 2, are evaluated.

TABLE 3 Preparation of Solutions Containing a High Concentration of Stannous Fluoride P:Sn Molar Ratio Amount (g) Percent in Solution 2 0.2 SnF₂  9% Solution remains 1.6 STPP 14% clear 15% STPP solution — 78% 2 0.2 SnF₂ 10% Solution is clear 0.2 STPP 16% upon 1.2 H₂O 74% preparation but becomes turbid overnight 2 0.2 SnF₂ 11% Does not form a 0.2 STPP 18% clear solution 1 H₂O 71%

As illustrated by the data described in Table 3 (above), only the solution containing 9% SnF₂ remains clear after 1 week at room temperature.

Example 4

A clear solution comprising 2% stannous fluoride (SnF₂) and sodium tripolyphosphate (STPP) with a P:Sn molar ratio of 5 is lyophilized using a Labconco FreeZone 2.5 Freeze Dryer. FTIR-ATR analysis is conducted on freeze dried powder on an extended range Spectrum One Perkin Elmer system featuring a CsI beam splitter, DTGS detector, and single-bounce diamond KRS-5 ATR crystal. Sample is placed directly on the ATR diamond. See FIG. 1. Peaks observed for the Sn-STPP complex are listed in Table 4 (broad peaks from water/ethanol at about 1640 and 3200 cm⁻¹ are omitted from peak table).

TABLE 4 Wavenumber Absorbance (cm⁻¹) (A) 512 0.9993 733 0.3144 883 0.6826 969 0.536 1081 0.4922

Ethanol is added dropwise to a clear solution comprising 2% stannous fluoride (SnF₂) and sodium tripolyphosphate (STPP) with a P:Sn molar ratio of 5 until precipitate forms. Solid is filtered and air dried. FTIR-ATR analysis is conducted on solid on an extended range Spectrum One Perkin Elmer system featuring a CsI beam splitter, DTGS detector, and single-bounce diamond KRS-5 ATR crystal. Sample is placed directly on the ATR diamond. See FIG. 2. An FTIR-ATR for solid SnF₂ is in FIG. 6.

FTIR-ATR analysis may be conducted on about 10-100 mg of solid.

Example 5

TABLE 5 P:Sn Molar Ratio Amount (g) pH Upon Preparation 1 0.2 SnCl₂•2H₂O Turbid 0.1 STPP 1.6 7.5 H₂O 2 0.2 SnCl₂•2H₂O Turbid 1.6 15% STPP solution 3.2 6.0 H₂O 3 0.2 SnCl₂•2H₂O Clear 2.5 15% STPP solution 4.4 5.2 H₂O 5 0.2 SnCl₂•2H₂O Clear 4.1 15% STPP solution 7.1 3.5 H₂O 10 0.2 SnCl₂•2H₂O Cloudy 1.2 STPP 7.7 6.4 H₂O 15 0.2 SnCl₂•2H₂O Turbid 1.8 STPP 7.4 5.8 H₂O

Upon preparation, the solutions with P/Sn molar ratios of 1, 2, and 15 appear turbid and the solution with a P/Sn molar ratio of 10 appears slightly cloudy. Only the solutions with P/Sn molar ratios of 3 and 5 are clear.

The solutions are aged overnight at room temperature. After 24 hours, the solutions containing a P/Sn molar ratio of 3 and 5 remain clear. The solutions with P/Sn molar ratios of 1, 2, and 15 are turbid and the solution with a P/Sn molar ratio of 10 appears slightly cloudy.

Example 6

Solutions of 2% SnF₂ and STPP in water with P/Sn molar ratios of 2, 5, and 10 are prepared. The solutions are analyzed as-prepared on an Agiltron PeakSeeker Raman System equipped with a fiber optic probe designed for liquid samples. The spectra, obtained in 30 second integration times, is compared to that of scintillation vials containing deionized water as a blank using RSIQ software. Raman spectra for the solutions are shown in FIG. 3 and peaks are listed in Table 6 (below).

TABLE 6 Raman Shift Sample (cm⁻¹) STPP 705 978 1022 1094 P/Sn 2 719 1084 P/Sn 5 719 978 1094 P/Sn 10 712 978 1094

Example 7

Solutions of 2% SnF₂ and STPP in water with P/Sn molar ratios of 2, 5, and 10 are prepared. 5 weight % D₂O is added to the solutions. ³¹P and ¹¹⁹Sn NMR are acquired on a Bruker AVANCE 500 spectrometer working at 202.4 MHz for ³¹P NMR and 163.5 MHz for ¹¹⁹Sn NMR at room temperature. ³¹P NMR are externally referenced to 85% H₃PO₄ set to 0 ppm. ¹¹⁹Sn NMR are externally referenced to saturated SnF₂ in D₂O at −796 ppm prepared right before measurement. FIGS. 4, A, 4, B, and 4, C depict ³¹P NMR spectra of solutions with P:Sn molar ratios of 10 (FIG. 4, A), 5 (FIG. 4, B), and 2 (FIG. 4, C). FIGS. 5, A, 5, B, and 5, C depict ¹¹⁹Sn NMR spectra of solutions with P:Sn molar ratios of 10 (FIG. 5, A), 5 (FIG. 5, B), and 2 (FIG. 5, C). ³¹P NMR peaks are listed in Table 7 and ¹¹⁹Sn NMR peaks are listed in Table 8. A ³¹P NMR spectrum of a solution of STPP in water with 5 weight % D₂O added and externally referenced to 85% H₃PO₄ set to 0 ppm is in FIG. 7.

TABLE 7 P/Sn Molar Ratio ³¹P Chemical Shift (ppm) SnF₂-STPP 10  2.21 −6.24 (doublet) −6.33 (doublet) −6.68 −19.08 (triplet) −19.17 (triplet) −19.27 (triplet) SnF₂-STPP 5  1.73 −7.27 −7.52 (doublet) −7.62 (doublet) −9.89 −10.37  −10.83  −11.62  −19.09 (triplet) −19.19 (triplet) −19.29 (triplet) SnF₂-STPP 2 −8.27 (doublet) −8.37 (doublet) −9.07 −17.69 (triplet) −17.79 (triplet) −17.89 (triplet)

TABLE 8 P/Sn Molar Ratio ¹¹⁹Sn Chemical Shift (ppm) SnF₂-STPP 10 −687.87 SnF₂-STPP 5 −684.61 −691.73 −699.51 −714.30 −717.32 −723.01 −725.28 −732.59 SnF₂-STPP 2 −714.97

Example 8

A toothpaste comprising the aqueous soluble tin phosphate complex as disclosed herein can be formulated as described in Table 9 below:

TABLE 9 Material Weight Percent Aqueous 2-30% soluble tin phosphate complex Water 2-50% Alkali 1-10%, e.g., 5% phosphate(s) pH Agent(s) 1-5%, e.g., 3% Abrasive(s) 10-30%, e.g., 20% Thickener(s) 1-5%, e.g., 3% Surfactant(s) 1-5%, e.g., 3% Humectant(s) 2-50% Flavoring(s) 1-5%, e.g., 3% Coloring(s) 0.1-2%, e.g., 1%

Example 9

A mouthwash comprising the aqueous soluble tin phosphate complex as disclosed herein can be formulated as described in Table 10 below:

TABLE 10 Material Weight Percent Aqueous  2-30% soluble tin phosphate complex Fluoride ion 0.01-1%, e.g., source(s) 0.05% Flavoring(s) 0.005-0.5%, e.g., 0.1-0.15% Humectant(s) 10-30%, e.g., 20% Surfactant(s) 0.1-1%, e.g., 0.4% Water 50-80% 

What is claimed is:
 1. An oral care composition comprising an aqueous soluble tin phosphate complex formed from a mixture comprising tin (II) fluoride or tin (II) chloride and a tripolyphosphate salt.
 2. The composition of claim 1, wherein the tripolyphosphate salt is sodium tripolyphosphate (Na₅P₃O₁₀).
 3. The composition of claim 1, wherein the complex is formed in situ in an aqueous solution and combined with the composition.
 4. The composition of claim 3, wherein the complex is isolated from the aqueous solution in solid form and combined with the composition.
 5. The composition of claim 1, wherein the complex is lyophilized and combined with the composition.
 6. The composition of claim 1, wherein the complex is isolated with an anti-solvent and combined with the composition.
 7. The composition of claim 1, wherein the complex is present in an amount of 2 to 30 weight % by weight of the composition.
 8. The composition of claim 1, wherein the complex is formed from tin (II) fluoride or tin (II) chloride and the tripolyphosphate salt in a molar ratio of 1P:1Sn to less than 15P:1Sn.
 9. The composition of claim 1, wherein the complex is formed from tin (II) fluoride or tin (II) chloride and the tripolyphosphate salt in a molar ratio of greater than 2P:1Sn to less than 10P:1Sn.
 10. The composition of claim 1, wherein the complex is formed from tin (II) fluoride or tin (II) chloride and the tripolyphosphate salt in a molar ratio of 2P:1Sn to 5P:1Sn.
 11. The composition of claim 1, wherein the complex is formed from tin (II) fluoride or tin (II) chloride and the tripolyphosphate salt in a molar ratio of 3P:1Sn to 5P:1Sn.
 12. The composition of claim 1, wherein the complex is formed from tin (II) fluoride or tin (II) chloride and the tripolyphosphate salt in a molar ratio of 5P:1Sn.
 13. The composition of claim 1, wherein the complex is formed from tin (II) fluoride or tin (II) chloride and sodium tripolyphosphate in a molar ratio of 1P:1Sn to less than 15P:1Sn.
 14. The composition of any one of claim 1, wherein the complex is formed from tin (II) fluoride or tin (II) chloride and sodium tripolyphosphate in a molar ratio of greater than 2P:1Sn to less than 10P:1Sn.
 15. The composition of any one of claim 1, wherein the complex is formed from tin (II) fluoride or tin (II) chloride and sodium tripolyphosphate in a molar ratio of 2P:1Sn to 5P:1Sn.
 16. The composition of claim 1, wherein the complex is formed from tin (II) fluoride or tin (II) chloride and sodium tripolyphosphate in a molar ratio of 3P:1Sn to 5P:1Sn.
 17. The composition of claim 1, wherein the complex is formed from tin (II) fluoride or tin (II) chloride and sodium tripolyphosphate in a molar ratio of 5P:1Sn.
 18. The composition of claim 1, wherein the complex is formed from a mixture comprising 1 to 10 weight % tin (II) fluoride or tin (II) chloride by weight of the mixture and 1 to 20 weight % tripolyphosphate salt by weight of the mixture.
 19. The composition of claim 1, wherein the complex is formed from a mixture comprising 1 to 10 weight % tin (II) fluoride or tin (II) chloride by weight of the mixture and 1 to 10 weight % tripolyphosphate salt by weight of the mixture.
 20. The composition of claim 1, wherein the complex is formed from a mixture comprising 1 to 10 weight % tin (II) fluoride or tin (II) chloride by weight of the mixture and 1 to 20 weight % sodium tripolyphosphate by weight of the mixture.
 21. The composition of claim 1, wherein the complex is formed from a mixture comprising 1 to 10 weight % tin (II) fluoride or tin (II) chloride by weight of the mixture and 1 to 10 weight % sodium tripolyphosphate by weight of the mixture.
 22. The composition of claim 1, wherein the composition comprises tin (II) fluoride.
 23. The composition of claim 1, wherein the composition comprises tin (II) chloride.
 24. The composition of claim 1, wherein the composition comprises an aqueous solution.
 25. The composition of claim 1 further comprising more than 20 weight % water by weight of the composition.
 26. The composition of claim 1, wherein the composition is a mouthwash.
 27. The composition of claim 1 for use to reduce dentinal hypersensitivity.
 28. A method to reduce or inhibit dentinal hypersensitivity, dental caries, gingivitis, or plaque in a person in need thereof comprising applying an effective amount of an oral care composition as claimed in claim 1 to teeth of the person. 